Haloketone refrigerant compositions and uses thereof

ABSTRACT

Disclosed herein are haloketone refrigerant or heat transfer fluid compositions that are useful in refrigeration or air conditioning apparatus or as heat transfer fluids. The compositions of the present invention are also useful in centrifugal compressor systems that employ two-stage compressors or single slab/single pass heat exchangers.

CROSS REFERENCE(S) TO RELATED APPLICATION(S)

This application claims the priority benefit of U.S. Provisional Application 60/549,978, filed Mar. 4, 2004, and U.S. Provisional Application 60/575,037, filed May 26, 2004, and U.S. Provisional Application 60/584,785, filed Jun. 29, 2004.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to compositions for use in refrigeration and air conditioning systems comprising at least one haloketone or combinations thereof. Further, the present invention relates to compositions for use in refrigeration and air-conditioning systems employing a centrifugal compressor comprising at least one haloketone or combinations thereof. The compositions of the present invention are useful in processes for producing refrigeration or heat or as heat transfer fluids.

2. Description of Related Art

The refrigeration industry has been working for the past few decades to find replacement refrigerants for the ozone depleting chlorofluorocarbons (CFCs) and hydrochlorofluorocarbons (HCFCs) being phased out as a result of the Montreal Protocol. The solution for most refrigerant producers has been the commercialization of hydrofluorocarbon (HFC) refrigerants. The new HFC refrigerants, HFC-134a being the most widely used at this time, have zero ozone depletion potential and thus are not affected by the current regulatory phase out as a result of the Montreal Protocol.

Further environmental regulations may ultimately cause global phase out of certain HFC refrigerants. Currently, the automobile industry is facing regulations relating to global warming potential for refrigerants used in mobile air-conditioning. Therefore, there is a great current need to identify new refrigerants with reduced global warming potential for the automobile air-conditioning market. Should the regulations be more broadly applied in the future, an even greater need will be felt for refrigerants that can be used in all areas of the refrigeration and air-conditioning industry.

Currently proposed replacement refrigerants for HFC-134a include HFC-152a, pure hydrocarbons such as butane or propane, or “natural” refrigerants such as CO₂ or ammonia. Many of these suggested replacements are toxic, flammable, and/or have low energy efficiency. Therefore, new alternatives are constantly being sought.

The object of the present invention is to provide novel refrigerant compositions and heat transfer fluids that provide unique characteristics to meet the demands of low or zero ozone depletion potential and lower global warming potential as compared to current refrigerants.

BRIEF SUMMARY OF THE INVENTION

The present invention relates to a haloketone refrigerant or heat transfer fluid selected from the group consisting of:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; -   1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; -   1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; -   1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; -   1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; -   1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; -   1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; -   2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; -   CF₃C(O)CBrFCF₂CF₃; -   CF₃C(O)CF₂CF₂CBrF₂; -   CBrF₂C(O)CF(CF₃)₂; -   CF₃C(O)CBr(CF₃)₂; -   CBrF₂CF₂C(O)CF₂CF₃; -   CF₃CBrFC(O)CF₂CF₃; -   CF₃CBrFC(O)CF₂CF₂CF₃; -   CF₃CF₂C(O)CBrFCF₂CF₃; -   CF₃CF₂C(O)CF₂CF₂CBrF₂; -   CF₃C(O)CBr(CF₃)CF₂CF₃; -   CF₃C(O)CF(CF₃)CBrFCF₃; -   CF₃C(O)CBrFCF₂CF₂CF₂CF₃; -   CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂; -   CF₃CBrFC(O)CF₂CF₂CF₂CF₃; -   CF₃CF₂C(O)CBrFCF₂CF₂CF₃; -   CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂; -   CF₃CF₂CBrFC(O)CF₂CF₂CF₃; -   CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃; -   CF₃CBrFC(O)CF(CF₃)CF₂CF₃; -   CF₃CF₂C(O)CBr(CF₃)CF₂CF₃; -   CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃; -   CBrF₂CF₂CF₂C(O)CF(CF₃)₂; -   CF₃CF₂CBrFC(O)CF(CF₃)₂; -   CF₃CF₂CF₂C(O)CBr(CF₃)₂; -   (CF₃)₂CBrC(O)CF(CF₃)₂; -   CF₃CBrFCF₂C(O)CF(CF₃)₂; -   CHF₂CF₂C(O)CBr(CF₃)₂; -   (CF₃)₂CHC(O)CBr(CF₃)₂; -   CHF₂CF₂C(O)CBrFCF₃; -   (CF₃)₂CHC(O)CBrFCF₃; -   (CF₃)₂CHC(O)CBrF₂; -   CBrF₂CF₂C(O)CH(CF₃)₂; -   CBrF₂C(O)CF(CF₃)OCF₃; -   CBrF₂CF₂C(O)CF(CF₃)OCF₃; -   CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃; -   CBrF₂C(O)CF(CF₃)OC₂F₅; -   CBrF₂CF₂C(O)CF(CF₃)OC₂F₅; -   CBrF₂C(O)CF(CF₃)OCF₂C₂F₅; -   CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅; -   CBrF₂C(O)CF(CF₃)OCF(CF₃)₂; -   CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂; -   CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; -   CF₃CBrFC(O)CF(CF₃)OCF₃; -   CF₃CBrFC(O)CF(CF₃)OC₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF₃; -   (CF₃)₂CBrC(O)CF(CF₃)OCF₃; -   CF₃CBrFC(O)CF(CF₃)OC₂F₅; -   (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; -   CBrF₂C(O)CF(OCF₂CHF₂)CF₃; -   CBrF₂C(O)CH(OCF₂CHF₂)CF₃; -   CBrF₂C(O)CF(OCH₃)CF₃; -   CBrF₂C(O)CF(CF₂OCH₃)CF₃; -   CClF₂CFBrC(O)CF₂CF₃; -   CBrF₂CFClC(O)CF₂CF₃; -   CClF₂CFBrC(O)CF(CF₃)₂; -   CBrF₂CFClC(O)CF(CF₃)₂; -   CClF₂CFBrC(O)CF(CF₃)(C₂F₅); -   CBrF₂CFClC(O)CF(CF₃)(C₂F₅); -   CClF₂C(O)CBr(CF₃)₂; -   CClF₂CF₂C(O)CBr(CF₃)₂; -   CF₃CClFC(O)CBr(CF₃)₂; -   CClF₂C(O)CBrFCF₃; -   CClF₂CF₂(O)CCBrFCF₃; -   CF₃CClFC(O)CBrFCF₃; -   CBrF₂C(O)CCl(CF₃)₂; -   CBrF₂CF₂C(O)CCl(CF₃)₂; -   CBrF₂C(O)CClFCF₃; -   CBrF₂CF₂C(O)CClFCF₃; and combinations thereof.

Disclosed herein also are the above listed compounds for use in refrigeration or air conditioning systems employing a centrifugal compressor, refrigeration or air conditioning systems employing a multi-stage centrifugal compressor, and/or employing a single slab/single pass heat exchanger, or refrigeration or air conditioning systems employing a 2-stage centrifugal compressor.

Also disclosed herein are processes for producing refrigeration, heat, and transfer of heat from a heat source to a heat sink using the present inventive compositions.

DETAILED DESCRIPTION OF THE INVENTION

The haloketone refrigerant compositions of the present invention comprise a single compound or a combination comprising more than one haloketone compound.

Compositions of the present invention have no ozone depletion potential and low global warming potential. For example, haloketones, alone or in mixtures will have global warming potentials lower than many HFC refrigerants currently in use.

The haloketones of the present invention are compounds containing fluorine, carbon, at least one ketone group oxygen, and optionally hydrogen, chlorine or bromine. Haloketones may be represented by the formula R³COR⁴, wherein R³ and R⁴ are independently selected from straight or branched chain, saturated or unsaturated, aliphatic or alicyclic fluorinated carbon radicals that may optionally-contain hydrogen, chlorine, or bromine. R³ and R⁴ may be joined to form a cyclic haloketone ring. The haloketones may contain from about 2 to 10 carbon atoms. Preferred haloketones contain 4 to 8 carbon atoms. The haloketones of the present invention may further contain heteroatoms, such as oxygen thus forming additional ketone groups, ether groups, aldehyde groups, or ester groups. Representative haloketones are listed in Table 1.

The bromofluoroketones of the present invention comprise at least one selected from the group consisting of: monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones. The following compounds are representative of the monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones of the present invention: CF₃C(O)CBrFCF₂CF₃, CF₃C(O)CF₂CF₂CBrF₂, CBrF₂C(O)CF(CF₃)₂, CF₃C(O)CBr(CF₃)₂, CBrF₂CF₂C(O)CF₂CF₃, CF₃CBrFC(O)CF₂CF₃, CF₃CBrFC(O)CF₂CF₂CF₃, CF₃CF₂C(O)CBrFCF₂CF₃, CF₃CF₂C(O)CF₂CF₂CBrF₂, CF₃C(O)CBr(CF₃)CF₂CF₃, CF₃C(O)CF(CF₃)CBrFCF₃, CF₃C(O)CBrFCF₂CF₂CF₂CF₃, CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂, CF₃CBrFC(O)CF₂CF₂CF₂CF₃, CF₃CF₂C(O)CBrFCF₂CF₂CF₃, CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂, CF₃CF₂CBrFC(O)CF₂CF₂CF₃, CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃, CF₃CBrFC(O)CF(CF₃)CF₂CF₃, CF₃CF₂C(O)CBr(CF₃)CF₂CF₃, CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃, CBrF₂CF₂CF₂C(O)CF(CF₃)₂, CF₃CF₂CBrFC(O)CF(CF₃)₂, CF₃CF₂CF₂C(O)CBr(CF₃)₂, (CF₃)₂CBrC(O)CF(CF₃)₂, CF₃CBrFCF₂C(O)CF(CF₃)₂, CHF₂CF₂C(O)CBr(CF₃)₂, (CF₃)₂CHC(O)CBr(CF₃)₂, CHF₂CF₂C(O)CBrFCF₃, (CF₃)₂CHC(O)CBrFCF₃, (CF₃)₂CHC(O)CBrF₂, CBrF₂CF₂C(O)CH(CF₃)₂, CBrF₂C(O)CF(CF₃)OCF₃, CBrF₂CF₂C(O)CF(CF₃)OCF₃, CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃, CBrF₂C(O)CF(CF₃)OC₂F₅, CBrF₂CF₂C(O)CF(CF₃)OC₂F₅, CBrF₂C(O)CF(CF₃)OCF₂C₂F₅, CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅, CBrF₂C(O)CF(CF₃)OCF(CF₃)₂, CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂, CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂, CF₃CBrFC(O)CF(CF₃)OCF₃, CF₃CBrFC(O)CF(CF₃)OC₂F₅, CF₃CBrFC(O)CF(CF₃)OCF₃, (CF₃)₂CBrC(O)CF(CF₃)OCF₃, CF₃CBrFC(O)CF(CF₃)OC₂F₅, (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅, CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅, CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂, CBrF₂C(O)CF(OCF₂CHF₂)CF₃, CBrF₂C(O)CH(OCF₂CH F₂)CF₃, CBrF₂C(O)CF(OCH₃)CF₃, CBrF₂C(O)CF(CF₂OCH₃)CF₃, CClF₂CFBrC(O)CF₂CF₃, CBrF₂CFClC(O)CF₂CF₃, CClF₂CFBrC(O)CF(CF₃)₂, CBrF₂CFClC(O)CF(CF₃)₂, CClF₂CFBrC(O)CF(CF₃)(C₂F₅), CBrF₂CFClC(O)CF(CF₃)(C₂F₅), CClF₂C(O)CBr(CF₃)₂, CClF₂CF₂C(O)CBr(CF₃)₂, CF₃CClFC(O)CBr(CF₃)₂, CClF₂C(O)CBrFCF₃, CClF₂CF₂(O)CCBrFCF₃, CF₃CClFC(O)CBrFCF₃, CBrF₂C(O)CCl(CF₃)₂, CBrF₂CF₂C(O)CCl(CF₃)₂, CBrF₂C(O)CClFCF₃ and CBrF₂CF₂C(O)CClFCF₃. TABLE 1 Haloketones CAS Reg. Compound Chemical Formula Chemical Name No. PEIK CF₃CF₂C(O)CF(CF₃)₂ 1,1,1,2,2,4,5,5,5-nonafluoro-4- 756-13-8 (trifluoromethyl)-3-pentanone (or perfluoroethylisopropyl ketone) PMIK CF₃C(O)CF(CF₃)₂ 1,1,1,3,4,4,4-heptafluoro-3- 756-12-7 (trifluoromethyl)-2-butanone (or perfluoromethylisopropyl ketone) (CF₃)₂CFC(O)CF(CF₃)₂ 1,1,1,2,4,5,5,5-octafluoro-2,4- bis(trifluoromethyl)-3-pentanone CHF₂CF₂C(O)CF(CF₃)₂ 1,1,1,2,4,4,5,5-octafluoro-2- (trifluoromethyl)-3-pentanone CF₃CF₂CF₂COCF(CF₃)₂ 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2- (trifluoromethyl)-3-hexanone CF₃OCF₂— 1,1,2,2,4,5,5,5-octafluoro-1- CF₂C(O)CF(CF₃)₂ (trifluoromethoxy)-4-(trifluoromethyl)-3- pentanone CF₃CF₂C(O)CH(CF₃)₂ 1,1,1,2,2,5,5,5-octafluoro-4- 61637-91-0 (trifluoromethyl)-3-pentanone CF₃CF₂C(O)CCI(CF₃)₂ 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2- 83714-48-1 (trifluoromethyl)-3-pentanone CF₃C(O)CBrFCF₂CF₃ 3-bromo-1,1,1,3,4,4,5,5,5-nonafluoro-2- perfluoropentanone CHF₂CF₂C(O)CBrFCF₃ 2-bromo-1,1,1,2,4,4,5,5-octafluoro-3- pentanone

1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone PEIK) is commercially available from 3M™ (St. Paul, Minn.). 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone (PMIK); 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; and 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone may be prepared as described in U.S. Pat. No. 6,478,979 incorporated herein by reference. 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone may be prepared from “HFP dimer” as described by England in Journal of Organic Chemistry, volume 49(no. 21), pages 4007 to 4008 (1984). 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone may be prepared as described by Saloutina, et al. in Izvestiya Adademii Nauk SSSR, Seriya Khimicheskaya, pages 1893 to 1896 (1982).

The bromofluoroketones of the present invention described previously including monobromoperfluoroketones, monohydromonobromoperfluoroketones, (perfluoroalkoxy)monobromoperfluoroketones, (fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones can be prepared as described in the following.

Monobromoperfluoroketones CF₃C(O)CF₂CF₂CBrF₂, CF₃CF₂C(O)CF₂CF₂CBrF₂ and CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂ of the present invention may be prepared by bromination of the corresponding monohydroperfluoroketones by the technique of Kolenko and Plashkin in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 1648 to 1650 (1977), and by Zapevalov, et al. in Zhurnal Organicheskoi Khimii, Vol. 26, pages 265 to 272 (1990). CF₃C(O)CF₂CF₂CBrF₂ may be prepared by bromination of monohydroperfluoroketone CF₃C(O)CF₂CF₂CHF₂, which may be prepared by isomerization of an epoxide as described by Zapelov et al. in Zhurnal Vsesoyuznogo Khimicheskogo Obshchestva im. D. I. Mendeleeva, Vol.18, pages 591 to 593 (1973). CF₃CF₂C(O)CF₂CF₂CBrF₂ and CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂ may be prepared by bromination of monohydroperfluoroketones CF₃CF₂C(O)CF₂CF₂CHF₂ and CF₃C(O)CF₂CF₂CF₂CF₂CHF₂, respectively, by the technique of Saloutina, et al. in Zhurnal Organicheskoi Khimii, Vol. 29, pages 1325 to 1336 (1993).

Preparation of monobromoperfluoroketones CF₃C(O)CF₂CF₂CBrF₂, CF₃CF₂C(O)CF₂CF₂CBrF₂ and CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂ of the present invention by conversion of the monohydroperfluoroketone terminal C—H bond to a terminal C—Br may be carried out using brominating agents such as elemental bromine, phosphorous pentabromide, or a mixture of bromine and phosphorous tribromide. The preferred brominating agent is a mixture of bromine and phosphorous tribromide.

Reaction of a monohydroperfluoroketone and a brominating agent may be carried out under substantially anhydrous conditions in the vapor phase or liquid phase in a container fabricated from materials of construction suitable for contact with bromine and hydrogen bromide at temperatures of about 300° C. to 600° C. Examples of such materials of construction include metallic alloys containing a nickel such as, for example, Hastelloy™ C and Hastelloy™ B. The reaction takes place under the autogenous pressures of the reactants at the reaction temperature.

The ratio of the brominating agent to the monohydroperfluoroketones is at least about 1 mole of brominating agent per mole of monohydroperfluoroketone and preferably about 1.3 moles of brominating agent per mole of monohydroperfluoroketone. More than 1.7 moles of brominating agent per mole of monohydroperfluoroketone provides little benefit.

Brominating the monohydroperfluoroketone may be conducted at temperatures of from about 300° C. to about 600° C. Using the preferred brominating agent, the temperature is preferably conducted from about 300° C. to 350° C. Contact times between the brominating agent and the monohydroperfluoroketone may be from about one hour to about twenty hours.

At the end of the contact period the reaction mixture is cooled and then treated with a reagent to decompose the brominating agent such as sodium sulfite. The monobromoperfluoroketone may be isolated by collecting the organic phase followed by distillation.

Monobromoperfluoroketones CF₃CF₂C(O)CBrFCF₂CF₃, CF₃CF₂CBrFC(O)CF(CF₃)₂, (CF₃)₂CBrC(O)CF(CF₃)₂, CF₃CF₂C(O)CBr(CF₃)CF₂CF₃ and CF₃CBrFC(O)CF(CF₃)CF₂CF₃, as well as mixtures of monobromoperfluoroketones of the present invention CF₃C(O)CBrFCF₂CF₃ and CF₃CBrFC(O)CF₂CF₃, or CF₃C(O)CBrFCF₂CF₂CF₂CF₃ and CF₃CBrFC(O)CF₂CF₂CF₂CF₃, or CF₃CF₂C(O)CBrFCF₂CF₂CF₃ and CF₃CF₂CBrFC(O)CF₂CF₂CF₃, may be prepared by contacting perfluoroolefin epoxides, such as the epoxide of perfluoro-2-pentene, perfluoro-2-heptene, or perfluoro-3-heptene, with an alkali metal bromide as described by Saloutina et al. in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 1893 to 1896 (1982). The perfluoroolefin epoxides may be prepared by contacting perfluoroolefin with an alkali metal hypohalite as described by Kolenko, et al. in Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, pages 2509-2512 (1979).

The contact of perfluoroolefin epoxides with alkali metal bromides may be carried out in a polar non-protic solvent such as glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and alkane nitriles such as acetonitrile, propionitrile, and butyronitrile. Preferred solvents for contacting perfluoroolefin epoxides with alkali metal bromides are glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether, and alkane nitriles such as acetonitrile, propionitrile, and butyronitrile.

Alkali metal bromides suitable for opening the perfluoroolefin epoxide ring and formation of a C—Br bond include lithium bromide, sodium bromide, potassium bromide, and cesium bromide; sodium and lithium bromide are preferred.

The mole ratio of the alkali metal bromide to the perfluoroolefin epoxide is at least about 2:1, preferably about 10:1.

Reaction of alkali metal bromides and perfluoolefin epoxide may be conducted in the liquid phase under substantially anhydrous conditions at temperatures of from about 10° C. to about 150° C., with contact times of from about 0.5 hour to about thirty-six hours. Specific pressure conditions are not critical.

At the end of the contact period the reaction mixture may be distilled to isolate the monobromoperfluoroketone.

Monobromoperfluoroketones of the present invention CBrF₂C(O)CF(CF₃)₂, CBrF₂CF₂C(O)CF₂CF₃, CF₃CBrFCF₂C(O)CF(CF₃)₂, CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂, CBrF₂CF₂CF₂C(O)CF(CF₃)₂, and CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃ may be prepared by reacting a monobromoperfluoroacyl fluoride with a perfluoroolefin.

CBrF₂C(O)CF(CF₃)₂ may be prepared by reacting CBrF₂C(O)F with CF₃CF═CF₂; CBrF₂CF₂C(O)CF₂CF₃ may be prepared by reacting CBrF₂CF₂C(O)F with CF₂═CF₂; CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂ may be prepared by reacting CBrF₂CF₂CF₂CF₂C(O)F with CF₂═CF₂; CBrF₂CF₂CF₂C(O)CF(CF₃)₂ may be prepared by reacting CBrF₂CF₂CF₂C(O)F with CF₃CF═CF₂; CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃ may be prepared by reacting CBrF₂CF₂C(O)F with CF₃CF═CFCF₃; and CF₃CBrFCF₂C(O)CF(CF₃)₂ may be prepared by reacting CF₃CBrFCF₂C(O)F with CF₃CF═CF₂.

Monobromoperfluoroketones of the present invention CF₃C(O)CBr(CF₃)₂, CF₃CBrFC(O)CF₂CF₂CF₃, CF₃C(O)CBr(CF₃)CF₂CF₃, CF₃C(O)CF(CF₃)CBrFCF₃, CF₃CF₂CF₂C(O)CBr(CF₃)₂, may be prepared by reacting a perfluoroacyl fluoride with a monobromoperfluoroolefin.

CF₃C(O)CBr(CF₃)₂ may be prepared by reacting CF₃C(O)F with CF₃CBr═CF₂; CF₃CBrFC(O)CF₂CF₂CF₃ may be prepared by reacting CBrF═CF₂ with CF₃CF₂CF₂C(O)F; a mixture of CF₃C(O)CBr(CF₃)CF₂CF₃ and CF₃C(O)CF(CF₃)CBrFCF₃ may be prepared by reacting CF₃CBr═CFCF₃ with CF₃C(O)F; and CF₃CF₂CF₂C(O)CBr(CF₃)₂ may be prepared by reacting CF₃CF₂CF₂C(O)F with CF₃CBr═CF₂.

(Perfluoroalkoxy)monobromoperfluoroketones of the present invention are of the formula R¹C(O)CF(CF₃)OR^(F), wherein R¹ is a C₁ to C₃ monobromoperfluoroalkyl radical, and R^(F) is a C₁ to C₃ perfluoroalkyl radical, may be obtained by reacting monobromoperfluoroacyl fluorides of the formula R¹C(O)F with perfluorovinyl ethers of the formula CF₂═CFOR^(F). Representative (perfluoroalkoxy)monobromoperfluoroketones of the present invention include CBrF₂C(O)CF(CF₃)OCF₃, CBrF₂CF₂C(O)CF(CF₃)OCF₃, CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃, CBrF₂C(O)CF(CF₃)OC₂F₅, CBrF₂CF₂C(O)CF(CF₃)OC₂F₅, CBrF₂C(O)CF(CF₃)OCF₂C₂F₅, CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅, CBrF₂C(O)CF(CF₃)OCF(CF₃)₂, CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂, CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂, CF₃CBrFC(O)CF(CF₃)OCF₃, and CF₃CBrFC(O)CF(CF₃)OC₂F₅.

CBrF₂C(O)CF(CF₃)OCF₃ may be prepared by reacting CBrF₂C(O)F with CF₂═CFOCF₃; CBrF₂CF₂C(O)CF(CF₃)OCF₃ may be prepared by reacting CBrF₂CF₂C(O)F with CF₂═CFOCF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃ may be prepared by reacting CBrF₂CF₂CF₂C(O)F with CF₂═CFOCF₃; CBrF₂C(O)CF(CF₃)OC₂F₅ may be prepared by reacting CBrF₂C(O)F with CF₂═CFOC₂F₅; CBrF₂CF₂C(O)CF(CF₃)OC₂F₅ may be prepared by reacting CBrF₂CF₂C(O)F with CF₂═CFOC₂F₅; CBrF₂C(O)CF(CF₃)OCF₂C₂F₅ may be prepared by reacting CBrF₂C(O)F with CF₂═CFOCF₂C₂F₅; CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅ may be prepared by reacting CBrF₂CF₂C(O)F with CF₂═CFOCF₂C₂F₅; CBrF₂C(O)CF(CF₃)OCF(CF₃)₂ may be prepared by reacting CBrF₂C(O)F with CF₂═CFOCF(CF₃)₂; CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂ may be prepared by reacting CBrF₂CF₂C(O)F with CF₂═CFOCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF₃ may be prepared by reacting CF₃CBrFC(O)F with CF₂═CFOCF₃; and CF₃CBrFC(O)CF(CF₃)OC₂F₅ may be prepared by reacting CF₃CBrFC(O)F with CF₂═CFOC₂F₅.

(Perfluoroalkoxy)monobromoperfluoroketones of the formula R¹C(O)CF(CF₃)OR^(F) may also be obtained by reacting perfluoroalkoxyperfluoroacyl fluorides of the formula R^(F)OCF(CF₃)C(O)F with a monobromoperfluoroolefin. Representative (perfluoroalkoxy)monobromoperfluoroketones of the present invention include CF₃CBrFC(O)CF(CF₃)OCF₃, (CF₃)₂CBrC(O)CF(CF₃)OCF₃, CF₃CBrFC(O)CF(CF₃)OC₂F₅, (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅, CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅, and CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂.

CF₃CBrFC(O)CF(CF₃)OCF₃ may be prepared by reacting CF₃OC(CF₃)FC(O)F with CF₂═CBrF; (CF₃)₂CBrC(O)CF(CF₃)OCF₃ may be prepared by reacting CF₃OC(CF₃)FC(O)F with CF₃CBr═CF₂; CF₃CBrFC(O)CF(CF₃)OC₂F₅ may be prepared by reacting C₂F₅OC(CF₃)FC(O)F with CF₂═CBrF; (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅ may be prepared by reacting C₂F₅OC(CF₃)FC(O)F with CF₃CBr═CF₂; CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅ may be prepared by reacting C₂F₅CF₂OC(CF₃)FC(O)F with CF₂═CBrF; and CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂ may be prepared by reacting (CF₃)₂CFOC(CF₃)FC(O)F with CF₂═CBrF.

(Fluoroalkoxy)monobromoperfluoroketones of the present invention are of the formula R¹C(O)CX(CF₃)OR², wherein X is H or F, R¹ is a C₁, C₂, or C₃ bromoperfluoroalkyl radical, and R² is a C₁ to C₃ alkyl or fluoroalkyl radical, may be prepared by reacting monobromoperfluoroacyl fluorides of the formula R¹C(O)F with hydrofluorovinyl ethers of the formula CF₂═CXOR². Representative (fluoroalkoxy)monobromoperfluoroketones include CBrF₂C(O)CF(OCF₂CHF₂)CF₃, CBrF₂C(O)CH(OCF₂CHF₂)CF₃, CBrF₂C(O)CF(OCH₃)CF₃, and CBrF₂C(O)CF(CF₂OCH₃)CF₃.

CBrF₂C(O)CF(OCF₂CHF₂)CF₃ may be prepared by reacting CBrF₂C(O)F with CF₂═CFOCF₂CHF₂; CBrF₂C(O)CH(OCF₂CHF₂)CF₃ may be prepared by reacting CBrF₂C(O)F with CF₂═CHOCF₂CHF₂; and CBrF₂C(O)CF(OCH₃)CF₃ may be prepared by reacting CBrF₂C(O)F with CF₂═CFOCH₃.

Another (fluoroalkoxy)monobromoperfluoroketone of the present invention includes CBrF₂C(O)CF(CF₂OCH₃)CF₃, prepared by reacting CBrF₂C(O)F with CF₃CF═CFOCH₃.

The reaction of fluoroacyl fluorides with fluoroolefins is described by Fawcett, et al. in U.S. Pat. No. 3,185,734 and Journal of the American Chemical Society, Vol. 84, pages 4285 to 4288 (1962). The teachings of these references may be applied to the aforementioned preparation of monobromoperfluoroketones by the reaction of monobromoperfluoroacyl fluorides with perfluoroolefins as well as the aforementioned preparation of monobromoperfluoroketones by the reaction of perfluoroacyl fluorides with monobromoperfluoroolefins. These references may also be applied to the preparation of (perfluoroalkoxy)monobromoperfluoroketones by the reaction of monobromoperfluoroacyl fluorides with perfluorovinyl ethers, or by the reaction of perfluoroalkoxyperfluoroacyl fluorides with monobromoperfluoroolefins. These references may also be applied to the preparation of (fluoroalkoxy)monobromoperfluoroketones by the reaction of monobromoperfluoroacyl fluorides with hydrofluorovinyl ethers.

Though not essential for preparing the ketones of the present invention, reaction of a fluoroacyl fluoride (such as a perfluoroacyl fluoride or monobromoperfluoroacyl fluoride) with a fluoroolefin (such as a perfluoroolefin, monobromoperfluoroolefin, perfluorovinyl ether or hydrofluorovinyl ether) may be performed in a polar non-protic solvent such as N,N-dimethyl formamide, N,N-dimethyl acetamide, dimethyl sulfolane, dimethylsulfoxide, N-methylpyrrolidinone, and glycol ethers such as ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, and tetraethylene glycol dimethyl ether. Preferred solvents for reacting fluoroacyl fluorides with fluoroolefin are glycol ethers. The reaction may be run under substantially anhydrous conditions.

The mole ratio of the fluoroolefin to fluoroacyl fluoride during the reaction may be at least about 1:1 to about 2:1, and preferably is about 1.1.

The reaction of fluoroacyl fluoride with fluoroolefin is preferably conducted in the presence of a fluoride ion source such as an alkali metal fluoride, alkali metal hydrogen difluoride (i.e., a bifluoride), alkali-earth metal fluoride, tetraalkylammonium fluoride, tetraalkylammonium hydrogen fluoride, trialkylammonium fluoride, or non-oxidizing transition metal fluorides. Preferred fluoride ion sources are potassium fluoride, cesium fluoride, and potassium bifluoride. The fluoride ion source may be present at a level of 5 mole percent to 20 mole percent, preferably about 10 mole percent, based on the quantity of fluoroolefin present.

Temperatures of from about 50° C. to about 250° C., preferably from about 100° C. to about 150° C. are effective to produce any of the fluorinated ketones of the present invention by reaction of a fluoroacyl fluoride with a fluoroolefin.

The reaction of fluoroacyl fluoride with fluoroolefin may take place in batch mode or in semi-batch mode with the fluoroacyl fluoride added gradually to the mixture of the fluoroolefin, solvent, and fluoride ion source. Contact times suitable for the reaction may be from about 0.5 hour to about 24 hours. The reaction typically takes place under autogenous pressure provided by the reactants at the reaction temperature.

Though not added intentionally to the reactions, hydrogen fluoride may be present in small amounts during the reactions of fluoroacyl fluorides due to the presence of traces of water. Reaction of fluoroacyl fluorides with fluoroolefins may be conducted in a vessel formed of materials compatible with hydrogen fluoride at elevated temperatures and pressures. Examples of such materials include stainless steels, in particular of the austenitic type, the well-known high nickel alloys, such as Monel™ nickel-copper alloys, Hastelloy™ nickel-based alloys and, Inconel™ nickel-chromium alloys, and copper-clad steel.

The haloketone products may be isolated from the reaction mixture as a lower liquid layer or by distillation. After removing traces of fluoride salts by washing with water, such products may be purified by distillation.

The present invention further includes monohydromonobromoperfluoroketones in which one of the C—F bonds in a perfluoroketone has been replaced by a C—Br bond, and in addition, another of the C—F bonds in said perfluoroketone has been replaced by a C—H bond. Monohydromonobromoperfluoroketones of the present invention comprise CHF₂CF₂C(O)CBrFCF₃, (CF₃)₂CHC(O)CBrFCF₃, CHF₂CF₂C(O)CBr(CF₃)₂, (CF₃)₂CHC(O)CBr(CF₃)₂, (CF₃)₂CHC(O)CBrF₂ and CBrF₂CF₂C(O)CH(CF₃)₂.

CHF₂CF₂C(O)CBrFCF₃ may be prepared by reacting CHF₂CF₂C(O)F with CBrF═CF₂; (CF₃)₂CHC(O)CBrFCF₃ may be prepared by reacting (CF₃)₂CHC(O)F with CBrF═CF₂; CHF₂CF₂C(O)CBr(CF₃)₂ may be prepared by reacting CHF₂CF₂C(O)F with CF₃CBr═CF₂; (CF₃)₂CHC(O)CBr(CF₃)₂ may be prepared by reacting (CF₃)₂CHC(O)F with CF₃CBr═CF₂; and CBrF₂CF₂C(O)CH(CF₃)₂ may be prepared by reacting CBrF₂CF₂C(O)F with CF₃CH═CF₂. The monohydromonobromoperfluoroketone (CF₃)₂CHC(O)CBrF₂ may be prepared by the reaction of the bromofluoroacyl fluoride CBrF₂C(O)F with the monohydroperfluoroolefin CF₃CH═CF₂.

The production of monohydromonobromoperfluoroketones by the reaction of monohydroperfluoroacyl fluorides with monobromoperfluoroolefins, as well as by the reaction of monobromoperfluoroacyl fluorides with monohydroperfluoroolefins, may use reaction conditions and procedure similar to those discussed hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin.

The present invention further comprises monochloromonobromoperfluoroketones in which one of the C—F bonds in a perfluoroketone has been replaced by a C—Br bond, and in addition, another one of the C—F bonds in said perfluoroketone has been replaced by a C—Cl bond. Monochloromonobromoperfluoroketones of the present invention comprise compounds of the formula CXF₂CFYC(O)CFRCF₃, wherein X is Cl and Y is Br, or wherein X is Br and Y is Cl, and wherein R is F, a CF₃ radical, or a C₂F₅ radical. These compounds may be prepared by contacting an acid fluoride of the formula CXF₂CFYC(O)F, prepared as disclosed by Darst, et al. in U.S. Pat. No. 5,557,010, with a perfluoroolefin of the formula CFR═CFR. Representative monochloromonobromoperfluoroketones include CClF₂CFBrC(O)CF₂CF₃, prepared by reacting CClF₂CFBrC(O)F with CF₂═CF₂; CBrF₂CClFC(O)CF₂CF₃, prepared by reacting CBrF₂CClFC(O)F with CF₂═CF₂; CClF₂CFBrC(O)CF(CF₃)₂, prepared by reacting CClF₂CFBrC(O)F with CF₂═CFCF₃; and CBrF₂CClFC(O)CF(CF₃)₂, prepared by reacting CBrF₂CClFC(O)F with CF₂═CFCF₃.

Monochloromonobromoperfluoroketones of the present invention further comprise CClF₂C(O)CBr(CF₃)₂, CClF₂CF₂C(O)CBr(CF₃)₂, CF₃CClFC(O)CBr(CF₃)₂, CClF₂C(O)CBrFCF₃, CClF₂CF₂C(O)CBrFCF₃, and CF₃CClFC(O)CBrFCF₃ which may be prepared by reacting a monochloroperfluoroacyl fluoride with a monobromoperfluoroolefin.

CClF₂C(O)CBr(CF₃)₂ may be prepared by reacting CClF₂C(O)F with CF₃CBr═CF₂; CClF₂CF₂C(O)CBr(CF₃)₂ may be prepared by reacting CClF₂CF₂C(O)F with CF₃CBr═CF₂; CF₃CClFC(O)CBr(CF₃)₂ may be prepared by reacting CF₃CClFC(O)F with CF₃CBr═CF₂; CClF₂C(O)CBrFCF₃ may be prepared by reacting CClF₂C(O)F with CF₂═CBrF; CClF₂CF₂C(O)CBrFCF₃ may be prepared by reacting CClF₂CF₂(O)F with CF₂═CBrF; CF₃CClFC(O)CBrFCF₃ may be prepared by reacting CF₃CClFC(O)F with CF₂═CBrF.

Monochloromonobromoperfluoroketones of the present invention further include CBrF₂C(O)CCl(CF₃)₂, CBrF₂CF₂C(O)CCl(CF₃)₂, CBrF₂C(O)CClFCF₃, and CBrF₂CF₂C(O)CClFCF₃ which may be prepared by reacting a monobromoperfluoroacyl fluoride with a monochloroperfluoroolefin.

CBrF₂C(O)CCl(CF₃)₂ may be prepared by reacting CBrF₂C(O)F with CF₃CCl═CF₂; CBrF₂CF₂C(O)CCl(CF₃)₂ may be prepared by reacting CBrF₂CF₂C(O)F with CF₃CCl═CF₂; CBrF₂C(O)CClFCF₃ may be prepared by reacting CBrF₂C(O)F with CF₂═CClF; and CBrF₂CF₂C(O)CClFCF₃ may be prepared by reacting CBrF₂CF₂C(O)F with CF₂═CClF.

The formation of monohydromonobromoperfluoroketones by the reaction of fluoroacyl fluorides of the formula CXF₂CFYC(O)F with perfluoroolefins, or by the reaction of monochloroperfluoroacyl fluorides with monobromoperfluoroolefins, or by the reaction of monobromoperfluoroacyl fluorides with monochloroperfluoroolefins, may use reaction conditions and procedure similar to those discussed hereinabove for the reaction of a fluoroacyl fluoride with a fluoroolefin.

The compositions may be prepared by any convenient method to combine the desired amounts of the individual components. A preferred method is to weigh the desired component amounts and thereafter combine the components in an appropriate vessel. Agitation may be used, if desired.

The refrigerant or heat transfer compositions of the present invention include:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; -   1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; -   1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; -   1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; -   1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; -   1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; -   1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; -   2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; -   CF₃C(O)CBrFCF₂CF₃; -   CF₃C(O)CF₂CF₂CBrF₂; -   CBrF₂C(O)CF(CF₃)₂; -   CF₃C(O)CBr(CF₃)₂; -   CBrF₂CF₂C(O)CF₂CF₃; -   CF₃CBrFC(O)CF₂CF₃; -   CF₃CBrFC(O)CF₂CF₂CF₃; -   CF₃CF₂C(O)CBrFCF₂CF₃; -   CF₃CF₂C(O)CF₂CF₂CBrF₂; -   CF₃C(O)CBr(CF₃)CF₂CF₃; -   CF₃C(O)CF(CF₃)CBrFCF₃; -   CF₃C(O)CBrFCF₂CF₂CF₂CF₃; -   CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂; -   CF₃CBrFC(O)CF₂CF₂CF₂CF₃; -   CF₃CF₂C(O)CBrFCF₂CF₂CF₃; -   CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂; -   CF₃CF₂CBrFC(O)CF₂CF₂CF₃; -   CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃; -   CF₃CBrFC(O)CF(CF₃)CF₂CF₃; -   CF₃CF₂C(O)CBr(CF₃)CF₂CF₃; -   CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃; -   CBrF₂CF₂CF₂C(O)CF(CF₃)₂; -   CF₃CF₂CBrFC(O)CF(CF₃)₂; -   CF₃CF₂CF₂C(O)CBr(CF₃)₂; -   (CF₃)₂CBrC(O)CF(CF₃)₂; -   CF₃CBrFCF₂C(O)CF(CF₃)₂; -   CHF₂CF₂C(O)CBr(CF₃)₂; -   (CF₃)₂CHC(O)CBr(CF₃)₂; -   CHF₂CF₂C(O)CBrFCF₃; -   (CF₃)₂CHC(O)CBrFCF₃; -   (CF₃)₂CHC(O)CBrF₂; -   CBrF₂CF₂C(O)CH(CF₃)₂; -   CBrF₂C(O)CF(CF₃)OCF₃; -   CBrF₂CF₂C(O)CF(CF₃)OCF₃; -   CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃; -   CBrF₂C(O)CF(CF₃)OC₂F₅; -   CBrF₂CF₂C(O)CF(CF₃)OC₂F₅; -   CBrF₂C(O)CF(CF₃)OCF₂C₂F₅; -   CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅; -   CBrF₂C(O)CF(CF₃)OCF(CF₃)₂; -   CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂; -   CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; -   CF₃CBrFC(O)CF(CF₃)OCF₃; -   CF₃CBrFC(O)CF(CF₃)OC₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF₃; -   (CF₃)₂CBrC(O)CF(CF₃)OCF₃; -   CF₃CBrFC(O)CF(CF₃)OC₂F₅; -   (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; -   CBrF₂C(O)CF(OCF₂CHF₂)CF₃; -   CBrF₂C(O)CH(OCF₂CHF₂)CF₃; -   CBrF₂C(O)CF(OCH₃)CF₃; -   CBrF₂C(O)CF(CF₂OCH₃)CF₃; -   CClF₂CFBrC(O)CF₂CF₃; -   CBrF₂CFClC(O)CF₂CF₃; -   CClF₂CFBrC(O)CF(CF₃)₂; -   CBrF₂CFClC(O)CF(CF₃)₂; -   CClF₂CFBrC(O)CF(CF₃)(C₂F₅); -   CBrF₂CFClC(O)CF(CF₃)(C₂F₅); -   CClF₂C(O)CBr(CF₃)₂; -   CClF₂CF₂C(O)CBr(CF₃)₂; -   CF₃CClFC(O)CBr(CF₃)₂; -   CClF₂C(O)CBrFCF₃; -   CClF₂CF₂(O)CCBrFCF₃; -   CF₃CClFC(O)CBrFCF₃; -   CBrF₂C(O)CCl(CF₃)₂; -   CBrF₂CF₂C(O)CCl(CF₃)₂; -   CBrF₂C(O)CClFCF₃; -   CBrF₂CF₂C(O)CClFCF₃; and combinations thereof.

The compositions of the present invention may further comprise about 0.01 weight percent to about 5 weight percent of a thermal stabilizer such as nitromethane.

The compositions of the present invention may further comprise an ultra-violet (UV) dye and optionally a solubilizing agent. The UV dye is a useful component for detecting leaks of the refrigerant composition by permitting one to observe the fluorescence of the dye under an ultra-violet light at the point of a leak within a refrigeration or air-conditioning system. Solubilizing agents may be needed due to poor solubility of such UV dyes in some refrigerants.

By “ultra-violet” dye is meant a UV fluorescent composition that absorbs light in the ultra-violet or “near” ultra-violet region of the electromagnetic spectrum. The fluorescence produced by the UV fluorescent dye under illumination by a UV light that emits radiation with wavelength anywhere from 10 nanometer to 750 nanometer may be detected. Therefore, if refrigerant containing such a UV fluorescent dye is leaking from a given point in a refrigeration or air conditioning apparatus, the fluorescence can be detected at the leak point. Such UV fluorescent dyes include but are not limited to naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, and derivatives or mixtures thereof.

Solubilizing agents of the present invention comprise at least one compound selected from the group consisting of hydrocarbons, hydrocarbon ethers, polyoxyalkylene glycol ethers, amides, nitriles, ketones, chlorocarbons, esters, lactones, aryl ethers, fluoroethers and 1,1,1-trifluoroalkanes.

Hydrocarbon solubilizing agents of the present invention comprise hydrocarbons including straight chained, branched chain or cyclic alkanes or alkenes containing 5 or fewer carbon atoms and only hydrogen with no other functional groups. Representative hydrocarbon solubilizing agents comprise propane, propylene, cyclopropane, n-butane, isobutane, and n-pentane. It should be noted that if the refrigerant is a hydrocarbon, then the solubilizing agent may not be the same hydrocarbon.

Hydrocarbon ether solubilizing agents of the present invention comprise ethers containing only carbon, hydrogen and oxygen, such as dimethyl ether (DME).

Polyoxyalkylene glycol ether solubilizing agents of the present invention are represented by the formula R¹[(OR²)_(x)OR³]_(y), wherein: x is an integer from 1-3; y is an integer from 1-4; R¹ is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R² is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R³ is selected from hydrogen and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹ and R³ is said hydrocarbon radical; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units. In the present polyoxyalkylene glycol ether solubilizing agents represented by R¹[(OR²)_(x)OR³]_(y): x is preferably 1-2; y is preferably 1; R¹ and R³ are preferably independently selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 4 carbon atoms; R² is preferably selected from aliphatic hydrocarbylene radicals having from 2 or 3 carbon atoms, most preferably 3 carbon atoms; the polyoxyalkylene glycol ether molecular weight is preferably from about 100 to about 250 atomic mass units, most preferably from about 125 to about 250 atomic mass units. The R¹ and R³ hydrocarbon radicals having 1 to 6 carbon atoms may be linear, branched or cyclic. Representative R¹ and R³ hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, and cyclohexyl. Where free hydroxyl radicals on the present polyoxyalkylene glycol ether solubilizing agents may be incompatible with certain compression refrigeration apparatus materials of construction (e.g. Mylar®), R¹ and R³ are preferably aliphatic hydrocarbon radicals having 1 to 4 carbon atoms, most preferably 1 carbon atom. The R² aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms form repeating oxyalkylene radicals—(OR²)_(x)—that include oxyethylene radicals, oxypropylene radicals, and oxybutylene radicals. The oxyalkylene radical comprising R² in one polyoxyalkylene glycol ether solubilizing agent molecule may be the same, or one molecule may contain different R² oxyalkylene groups. The present polyoxyalkylene glycol ether solubilizing agents preferably comprise at least one oxypropylene radical. Where R¹ is an aliphatic or alicyclic hydrocarbon radical having 1 to 6 carbon atoms and y bonding sites, the radical may be linear, branched or cyclic. Representative R¹ aliphatic hydrocarbon radicals having two bonding sites include, for example, an ethylene radical, a propylene radical, a butylene radical, a pentylene radical, a hexylene radical, a cyclopentylene radical and a cyclohexylene radical. Representative R¹ aliphatic hydrocarbon radicals having three or four bonding sites include residues derived from polyalcohols, such as trimethylolpropane, glycerin, pentaerythritol, 1,2,3-trihydroxycyclohexane and 1,3,5-trihydroxycyclohexane, by removing their hydroxyl radicals.

Representative polyoxyalkylene glycol ether solubilizing agents include but are not limited to: CH₃OCH₂CH(CH₃)O(H or CH₃)(propylene glycol methyl (or dimethyl)ether), CH₃O[CH₂CH(CH₃)O]₂(H or CH₃) (dipropylene glycol methyl (or dimethyl)ether), CH₃O[CH₂CH(CH₃)O]₃(H or CH₃)(tripropylene glycol methyl (or dimethyl)ether), C₂H₅OCH₂CH(CH₃)O(H or C₂H₅)(propylene glycol ethyl (or diethyl)ether), C₂H₅O[CH₂CH(CH₃)O]₂(H or C₂H₅)(dipropylene glycol ethyl (or diethyl) ether), C₂H₅O[CH₂CH(CH₃)O]₃(H or C₂H₅)(tripropylene glycol ethyl (or diethyl)ether), C₃H₇OCH₂CH(CH₃)O(H or C₃H₇)(propylene glycol n-propyl (or di-n-propyl)ether), C₃H₇O[CH₂CH(CH₃)O]₂(H or C₃H₇)(dipropylene glycol n-propyl (or di-n-propyl)ether), C₃H₇O[CH₂CH(CH₃)O]₃(H or C₃H₇) (tripropylene glycol n-propyl (or di-n-propyl)ether), C₄H₉OCH₂CH(CH₃)OH (propylene glycol n-butyl ether), C₄H₉O[CH₂CH(CH₃)O]₂(H or C₄H₉) (dipropylene glycol n-butyl (or di-n-butyl)ether), C₄H₉O[CH₂CH(CH₃)O]₃(H or C₄H₉)(tripropylene glycol n-butyl (or di-n-butyl)ether), CH₃)₃COCH₂CH(CH₃)OH(propylene glycol t-butyl ether), CH₃)₃CO[CH₂CH(CH₃)O]₂(H or (CH₃)₃)(dipropylene glycol t-butyl (or di-t-butyl)ether), (CH₃)₃CO[CH₂CH(CH₃)O]₃(H or (CH₃)₃)(tripropylene glycol t-butyl (or di-t-butyl)ether), C₅H₁₁OCH₂CH(CH₃)OH(propylene glycol n-pentyl ether), C₄H₉OCH₂CH(C₂H₅)OH(butylene glycol n-butyl ether), C₄H₉O[CH₂CH(C₂H₅)O]₂H(dibutylene glycol n-butyl ether), trimethylolpropane tri-n-butyl ether (C₂H₅C(CH₂O(CH₂)₃CH₃)₃) and trimethylolpropane di-n-butyl ether (C₂H₅C(CH₂OC(CH₂)₃CH₃)₂CH₂OH).

Amide solubilizing agents of the present invention comprise those represented by the formulae R¹CONR²R³ and cyclo-[R⁴CON(R⁵)—], wherein R¹, R², R³ and R⁵ are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; R⁴ is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units. The molecular weight of said amides is preferably from about 160 to about 250 atomic mass units. R¹, R², R³ and R⁵ may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹, R², R³ and R⁵ may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R¹⁻³, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Preferred amide solubilizing agents consist of carbon, hydrogen, nitrogen and oxygen. Representative R¹, R², R³ and R⁵aliphatic and alicyclic hydrocarbon radicals include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers. A preferred embodiment of amide solubilizing agents are those wherein R⁴ in the aforementioned formula cyclo-[R⁴CON(R⁵)—] may be represented by the hydrocarbylene radical (CR⁶R⁷)_(n), in other words, the formula: cyclo-[(CR⁶R⁷)_(n)CON(R⁵)—] wherein: the previously-stated values for molecular weight apply; n is an integer from 3 to 5; R⁵ is a saturated hydrocarbon radical containing 1 to 12 carbon atoms; R⁶ and R⁷ are independently selected (for each n) by the rules previously offered defining R¹⁻³. In the lactams represented by the formula: cyclo-[(CR⁶R⁷)_(n)CON(R⁵)—], all R⁶ and R⁷ are preferably hydrogen, or contain a single saturated hydrocarbon radical among the n methylene units, and R⁵ is a saturated hydrocarbon radical containing 3 to 12 carbon atoms. For example, 1-(saturated hydrocarbon radical)-5-methylpyrrolidin-2-ones.

Representative amide solubilizing agents include but are not limited to: 1-octylpyrrolidin-2-one, 1-decylpyrrolidin-2-one, 1-octyl-5-methylpyrrolidin-2-one, 1-butylcaprolactam, 1-cyclohexylpyrrolidin-2-one, 1-butyl-5-methylpiperid-2-one, 1-pentyl-5-methylpiperid-2-one, 1-hexylcaprolactam, 1-hexyl-5-methylpyrrolidin-2-one, 5-methyl-1-pentylpiperid-2-one, 1,3-dimethylpiperid-2-one, 1-methylcaprolactam, 1-butyl-pyrrolidin-2-one, 1,5-dimethylpiperid-2-one, 1-decyl-5-methylpyrrolidin-2-one, 1-dodecylpyrrolid-2-one, N,N-dibutylformamide and N,N-diisopropylacetamide.

Ketone solubilizing agents of the present invention comprise ketones represented by the formula R¹COR², wherein R¹ and R² are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units. R¹ and R² in said ketones are preferably independently selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 9 carbon atoms. The molecular weight of said ketones is preferably from about 100 to 200 atomic mass units. R¹ and R² may together form a hydrocarbylene radical connected and forming a five, six, or seven-membered ring cyclic ketone, for example, cyclopentanone, cyclohexanone, and cycloheptanone. R¹ and R² may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ and R² may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R¹ and R ², and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R¹ and R² aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R¹COR² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl.

Representative ketone solubilizing agents include but are not limited to: 2-butanone, 2-pentanone, acetophenone, butyrophenone, hexanophenone, cyclohexanone, cycloheptanone, 2-heptanone, 3-heptanone, 5-methyl-2-hexanone, 2-octanone, 3-octanone, diisobutyl ketone, 4-ethylcyclohexanone, 2-nonanone, 5-nonanone, 2-decanone, 4-decanone, 2-decalone, 2-tridecanone, dihexyl ketone and dicyclohexyl ketone.

Nitrile solubilizing agents of the present invention comprise nitriles represented by the formula R¹CN, wherein R¹ is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units. R¹ in said nitrile solubilizing agents is preferably selected from aliphatic and alicyclic hydrocarbon radicals having 8 to 10 carbon atoms. The molecular weight of said nitrile solubilizing agents is preferably from about 120 to about 140 atomic mass units. R¹ may optionally include substituted hydrocarbon radicals, that is, radicals containing non-hydrocarbon substituents selected from halogens (e.g., fluorine, chlorine) and alkoxides (e.g. methoxy). R¹ may optionally include heteroatom-substituted hydrocarbon radicals, that is, radicals, which contain the atoms nitrogen (aza-), oxygen (keto-, oxa-) or sulfur (thia-) in a radical chain otherwise composed of carbon atoms. In general, no more than three non-hydrocarbon substituents and heteroatoms, and preferably no more than one, will be present for each 10 carbon atoms in R¹, and the presence of any such non-hydrocarbon substituents and heteroatoms must be considered in applying the aforementioned molecular weight limitations. Representative R¹ aliphatic, alicyclic and aryl hydrocarbon radicals in the general formula R¹CN include pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers, as well as phenyl, benzyl, cumenyl, mesityl, tolyl, xylyl and phenethyl. Representative nitrile solubilizing agents include but are not limited to: 1-cyanopentane, 2,2-dimethyl-4-cyanopentane, 1-cyanohexane, 1-cyanoheptane, 1-cyanooctane, 2-cyanooctane, 1-cyanononane, 1-cyanodecane, 2-cyanodecane, 1-cyanoundecane and 1-cyanododecane.

Chlorocarbon solubilizing agents of the present invention comprise chlorocarbons represented by the formula RCl_(x), wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units. The molecular weight of said chlorocarbon solubilizing agents is preferably from about 120 to 150 atomic mass units. Representative R aliphatic and alicyclic hydrocarbon radicals in the general formula RCl_(x) include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, tert-pentyl, cyclopentyl, cyclohexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and their configurational isomers.

Representative chlorocarbon solubilizing agents include but are not limited to: 3-(chloromethyl)pentane, 3-chloro-3-methylpentane, 1-chlorohexane, 1,6-dichlorohexane, 1-chloroheptane, 1-chlorooctane, 1-chlorononane, 1-chlorodecane, and 1,1,1-trichlorodecane.

Ester solubilizing agents of the present invention comprise esters represented by the general formula R¹CO₂R², wherein R¹ and R² are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals. Preferred esters consist essentially of the elements C, H and O, have a molecular weight of from about 80 to about 550 atomic mass units.

Representative esters include but are not limited to: (CH₃)₂CHCH₂OOC(CH₂)₂₋₄OCOCH₂CH(CH₃)₂ (diisobutyl dibasic ester), ethyl hexanoate, ethyl heptanoate, n-butyl propionate, n-propyl propionate, ethyl benzoate, di-n-propyl phthalate, benzoic acid ethoxyethyl ester, dipropyl carbonate, “Exxate 700” (a commercial C₇ alkyl acetate), “Exxate 800” (a commercial C₈ alkyl acetate), dibutyl phthalate, and tert-butyl acetate.

Lactone solubilizing agents of the present invention comprise lactones represented by structures [A], [B], and [C]:

These lactones contain the functional group —CO₂— in a ring of six (A), or preferably five atoms (B), wherein for structures [A] and [B], R₁ through R₈ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R₁ though R₈ may be connected forming a ring with another R₁ through R₈. The lactone may have an exocyclic alkylidene group as in structure [C], wherein R₁ through R₆ are independently selected from hydrogen or linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals. Each R₁ though R₆ may be connected forming a ring with another R₁ through R₆. The lactone solubilizing agents have a molecular weight range of from about 80 to about 300 atomic mass units, preferred from about 80 to about 200 atomic mass units.

Representative lactone solubilizing agents include but are not limited to the compounds listed in Table 2. TABLE 2 Molecular Molecular Additive Molecular Structure Formula Weight (amu) (E,Z)-3-ethylidene-5-methyl- dihydro-furan-2-one

C₇H₁₀O₂ 126 (E,Z)-3-propylidefle-5-methyl- dihydro-furan-2-one

C₈H₁₂O₂ 140 (E,Z)-3-butylidene-5-methyl- dihydro-furan-2-one

C₉H₁₄O₂ 154 (E,Z)-3-pentylidene-5-methyl- dihydro-furan-2-one

C₁₀H₁₆O₂ 168 (E,Z)-3-Hexylidene-5-methyl- dihydro-furan-2-one

C₁₁H₁₈O₂ 182 (E,Z)-3-Heptylidene-5-methyl- dihydro-furan-2-one

C₁₂H₂₀O₂ 196 (E,Z)-3-octytidene-5-methyl- dihydro-furan-2-one

C₁₃H₂₂O₂ 210 (E,Z)-3-nonylidene-5-methyl- dihydro-furan-2-one

C₁₄H₂₄O₂ 224 (E,Z)-3-decylidene-5-methyl- dihydro-furan-2-one

C₁₅H₂₆O₂ 238 (E,Z)-3-(3,5,5-trimethylhexylidene)- 5-methyl-dihydrofuran-2-one

C₁₄H₂₄O₂ 224 (E,Z)-3-cyclohexylmethylidene-5- methyl-dihydrofuran-2-one

C₁₂H₁₈O₂ 194 gamma-octalactone

C₆H₁₄O₂ 142 gamma-nonalactone

C₉H₁₆O₂ 156 gamma-decalactone

C₁₀H₁₈O₂ 170 gamma-undecalactone

C₁₁H₂₀O₂ 184 gamma-dodecalactone

C₁₂H₂₂O₂ 198 3-hexyldihydro-furan-2-one

C₁₀H₁₈O₂ 170 3-heptyldihydro-furan-2-one

C₁₁H₂₀O₂ 184 cis-3-ethyl-5-methyl-dihydro-furan- 2-one

C₇H₁₂O₂ 128 cis-(3-propyl-5-methyl)-dihydro- furan-2-one

C₈H₁₄O₂ 142 cis-(3-butyl-5-methyl)-dihydro- furan-2-one

C₉H₁₆O₂ 156 cis-(3-pentyl-5-methyl)-dihydro- furan-2-one

C₁₀H₁₈O₂ 170 cis-3-hexyl-5-methyl-dihydro-furan- 2-one

C₁₁H₂₀O₂ 184 cis-3-heptyl-5-methyl-dihydro- furan-2-one

C₁₂H₂₂O₂ 198 cis-3-octyl-5-methyl-dihydro-furan- 2-one

C₁₃H₂₄O₂ 212 cis-3-(3,5,5-trimethytlhexyl)-5- methyl-dihydro-furan-2-one

C₁₄H₂₆O₂ 226 cis-3-cyclohexylmethyl-5-methyl- dihydro-furan-2-one

C₁₂H₂₀O₂ 196 5-methyl-5-hexyl-dihydro-furan-2- one

C₁₁H₂₀O₂ 184 5-methyl-5-octyl-dihydro-furan-2- one

C₁₃H₂₄O₂ 212 Hexahydro-isobenzofuran-1-one

C₈H₁₂O₂ 140 delta-decalactone

C₁₀H₁₈O₂ 170 delta-undecalactone

C₁₁H₂₀O₂ 184 delta-dodecalactone

C₁₂H₂₂O₂ 198 mixture of 4-hexyl-dihydrofuran-2- one and 3-hexyl-dihydro-furan-2- one

C₁₀H₁₈O₂ 170

Lactone solubilizing agents generally have a kinematic viscosity of less than about 7 centistokes at 40° C. For instance, gamma-undecalactone has kinematic viscosity of 5.4 centistokes and cis-(3-hexyl-5-methyl)dihydrofuran-2-one has viscosity of 4.5 centistokes both at 40° C. Lactone solubilizing agents may be available commercially or prepared by methods as described in U.S. patent application Ser. No. 10/910,495 (inventors being P. J. Fagan and C. J. Brandenburg), filed Aug. 3, 2004, incorporated herein by reference.

Aryl ether solubilizing agents of the present invention further comprise aryl ethers represented by the formula R¹OR², wherein: R¹ is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units. Representative R¹ aryl radicals in the general formula R¹OR² include phenyl, biphenyl, cumenyl, mesityl, tolyl, xylyl, naphthyl and pyridyl. Representative R² aliphatic hydrocarbon radicals in the general formula R¹OR² include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl and tert-butyl. Representative aromatic ether solubilizing agents include but are not limited to: methyl phenyl ether (anisole), 1,3-dimethyoxybenzene, ethyl phenyl ether and butyl phenyl ether.

Fluoroether solubilizing agents of the present invention comprise those represented by the general formula R¹OCF₂CF₂H, wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative fluoroether solubilizing agents include but are not limited to: C₈H₁₇OCF₂CF₂H and C₆H₁₃OCF₂CF₂H. It should be noted that if the refrigerant is a fluoroether, then the solubilizing agent may not be the same fluoroether.

1,1,1-Trifluoroalkane solubilizing agents of the present invention comprise 1,1,1-trifluoroalkanes represented by the general formula CF₃R¹, wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms, preferably primary, linear, saturated, alkyl radicals. Representative 1,1,1-trifluoroalkane solubilizing agents include but are not limited to: 1,1,1-trifluorohexane and 1,1,1-trifluorododecane.

Solubilizing agents of the present invention may be present as a single compound, or may be present as a mixture of more than one solubilizing agent. Mixtures of solubilizing agents may contain two solubilizing agents from the same class of compounds, say two lactones, or two solubilizing agents from two different classes, such as a lactone and a polyoxyalkylene glycol ether.

In the present compositions comprising refrigerant and UV fluorescent dye, from about 0.001 weight percent to about 1.0 weight percent of the composition is UV dye, preferably from about 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.

Solubility of these UV fluorescent dyes in refrigerants may be poor. Therefore, methods for introducing these dyes into the refrigeration or air conditioning apparatus have been awkward, costly and time consuming. U.S. Pat. No. RE 36,951 describes a method, which utilizes a dye powder, solid pellet or slurry of dye that may be inserted into a component of the refrigeration or air conditioning apparatus. As refrigerant and lubricant are circulated through the apparatus, the dye is dissolved or dispersed and carried throughout the apparatus. Numerous other methods for introducing dye into a refrigeration or air conditioning apparatus are described in the literature.

Ideally, the UV fluorescent dye could be dissolved in the refrigerant itself thereby not requiring any specialized method for introduction to the refrigeration or air conditioning apparatus. The present invention relates to compositions including UV fluorescent dye, which may be introduced into the system dissolved in the refrigerant. The inventive compositions will allow the storage and transport of dye-containing refrigerant even at low temperatures while maintaining the dye in solution.

In the present compositions comprising refrigerant, UV fluorescent dye and solubilizing agent, from about 1 to about 50 weight percent, preferably from about 2 to about 25 weight percent, and most preferably from about 5 to about 15 weight percent of the combined composition is solubilizing agent in the refrigerant. In the compositions of the present invention the UV fluorescent dye is present in a concentration from about 0.001 weight percent to about 1.0 weight percent in the refrigerant, preferably from 0.005 weight percent to about 0.5 weight percent, and most preferably from 0.01 weight percent to about 0.25 weight percent.

Optionally, commonly used refrigeration system additives may optionally be added, as desired, to compositions of the present invention in order to enhance performance and system stability. These additives are known within the field of refrigeration, and include, but are not limited to, anti wear agents, extreme pressure lubricants, corrosion and oxidation inhibitors, metal surface deactivators, free radical scavengers, and foam control agents,. In general, these additives are present in the inventive compositions in small amounts relative to the overall composition. Typically concentrations of from less than about 0.1 weight percent to as much as about 3 weight percent of each additive are used. These additives are selected on the basis of the individual system requirements. These additives include members of the triaryl phosphate family of EP (extreme pressure) lubricity additives, such as butylated triphenyl phosphates (BTPP), or other alkylated triaryl phosphate esters, e.g. Syn-0-Ad 8478 from Akzo Chemicals, tricrecyl phosphates and related compounds. Additionally, the metal dialkyl dithiophosphates (e.g. zinc dialkyl dithiophosphate (or ZDDP), Lubrizol 1375 and other members of this family of chemicals may be used in compositions of the present invention. Other antiwear additives include natural product oils and asymmetrical polyhydroxyl lubrication additives, such as Synergol TMS (International Lubricants). Similarly, stabilizers such as anti oxidants, free radical scavengers, and water scavengers may be employed. Compounds in this category can include, but are not limited to, butylated hydroxy toluene (BHT) and epoxides.

Solubilizing agents such as ketones may have an objectionable odor, which can be masked by addition of an odor masking agent or fragrance. Typical examples of odor masking agents or fragrances may include Evergreen, Fresh Lemon, Cherry, Cinnamon, Peppermint, Floral or Orange Peel or sold by Intercontinental Fragrance, as well as d-limonene and pinene. Such odor masking agents may be used at concentrations of from about 0.001% to as much as about 15% by weight based on the combined weight of odor masking agent and solubilizing agent.

The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions further comprising ultraviolet fluorescent dye, and optionally, solubilizing agent, in refrigeration or air conditioning apparatus. The method comprises introducing the refrigerant or heat transfer fluid composition into the refrigeration or air conditioning apparatus. This may be done by dissolving the UV fluorescent dye in the refrigerant or heat transfer fluid composition in the presence of a solubilizing agent and introducing the combination into the apparatus. Alternatively, this may be done by combining solubilizing agent and and UV fluorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid. The resulting composition is may be used in the refrigeration or air conditioning apparatus.

The present invention further relates to a method of using the refrigerant or heat transfer fluid compositions comprising ultraviolet fluorescent dye to detect leaks. The presence of the dye in the compostions allows for detection of leaking refrigerant in the refrigeration or air conditioning apparatus. Leak detection helps to address, resolve or prevent inefficient operation of the apparatus or system or equipment failure. Leak detection also helps one contain chemicals used in the operation of the apparatus.

The method comprises providing the composition comprising refrigerant, ultra-violet fluorescent dye as described herein, and optionally, a solubilizing agent as described herein, to refrigeration and air conditioning apparatus and employing a sutiable means for detecting the UV fluorescent dye-containing refrigerant. Suitable means for detecting the dye include, but are not limited to, ultra-violet lamp, often referred to as a “black light” or “blue light”. Such ultra-violet lamps are commercially available from numerous sources specifically designed for this purpose. Once the ultra-violet fluorescent dye containing composition has been introduced to the refrigeration or air conditioning apparatus and has been allowed to circulate throughout the system, a leak can be found by shining said ultra-violet lamp on the apparatus and observing the fluorescence of the dye in the vicinity of any leak point.

The present invention further relates to a method of using the compositions of the present invention for producing refrigeration or heat, wherein the method comprises producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition; or producing heat by condensing the said composition in the vicinity of the body to be heated and thereafter evaporating said composition.

Mechanical refrigeration is primarily an application of thermodynamics wherein a cooling medium, such as a refrigerant, goes through a cycle so that it can be recovered for reuse. Commonly used cycles include vapor-compression, absorption, steam-jet or steam-ejector, and air.

Vapor-compression refrigeration systems include an evaporator, a compressor, a condenser, and an expansion device. A vapor-compression cycle re-uses refrigerant in multiple steps producing a cooling effect in one step and a heating effect in a different step. The cycle can be described simply as follows. Liquid refrigerant enters an evaporator through an expansion device, and the liquid refrigerant boils in the evaporator at a low temperature to form a gas and produce cooling. The low-pressure gas enters a compressor where the gas is compressed to raise its pressure and temperature. The higher-pressure (compressed) gaseous refrigerant then enters the condenser in which the refrigerant condenses and discharges its heat to the environment. The refrigerant returns to the expansion device through which the liquid expands from the higher-pressure level in the condenser to the low-pressure level in the evaporator, thus repeating the cycle.

There are various types of compressors that may be used in refrigeration applications. Compressors can be generally classified as reciprocating, rotary, jet, centrifugal, scroll, screw or axial-flow, depending on the mechanical means to compress the fluid, or as positive-displacement (e.g., reciprocating, scroll or screw) or dynamic (e.g., centrifugal or jet), depending on how the mechanical elements act on the fluid to be compressed.

Either positive displacement or dynamic compressors may be used in the present inventive process. A centrifugal type compressor is the preferred equipment for the present refrigerant compositions.

A centrifugal compressor uses rotating elements to accelerate the refrigerant radially, and typically includes an impeller and diffuser housed in a casing. Centrifugal compressors usually take fluid in at an impeller eye, or central inlet of a circulating impeller, and accelerate it radially outward. Some static pressure rise occurs in the impeller, but most of the pressure rise occurs in the diffuser section of the casing, where velocity is converted to static pressure. Each impeller-diffuser set is a stage of the compressor. Centrifugal compressors are built with from 1 to 12 or more stages, depending on the final pressure desired and the volume of refrigerant to be handled.

The pressure ratio, or compression ratio, of a compressor is the ratio of absolute discharge pressure to the absolute inlet pressure. Pressure delivered by a centrifugal compressor is practically constant over a relatively wide range of capacities.

Positive displacement compressors draw vapor into a chamber, and the chamber decreases in volume to compress the vapor. After being compressed, the vapor is forced from the chamber by further decreasing the volume of the chamber to zero or nearly zero. A positive displacement compressor can build up a pressure, which is limited only by the volumetric efficiency and the strength of the parts to withstand the pressure.

Unlike a positive displacement compressor, a centrifugal compressor depends entirely on the centrifugal force of the high-speed impeller to compress the vapor passing through the impeller. There is no positive displacement, but rather what is called dynamic-compression.

The pressure a centrifugal compressor can develop depends on the tip speed of the impeller. Tip speed is the speed of the impeller measured at its tip and is related to the diameter of the impeller and its revolutions per minute. The capacity of the centrifugal compressor is determined by the size of the passages through the impeller. This makes the size of the compressor more dependent on the pressure required than the capacity.

Because of its high-speed operation, a centrifugal compressor is fundamentally a high volume, low-pressure machine. A centrifugal compressor works best with a low-pressure refrigerant, such as trichlorofluoromethane (CFC-11) or 1,2,2-trichlorotrifluoroethane (CFC-113).

Large centrifugal compressors typically operate at 3000 to 7000 revolutions per minute (rpm). Small turbine centrifugal compressors are designed for high speeds, from about 40,000 to about 70,000 (rpm), and have small impeller sizes, typically less than 0.15 meters.

A multi-stage impeller may be used in a centrifugal compressor to improve compressor efficiency thus requiring less power in use. For a two-stage system, in operation, the discharge of the first stage impeller goes to the suction intake of a second impeller. Both impellers may operate by use of a single shaft (or axle). Each stage can build up a compression ratio of about 4 to 1; that is, the absolute discharge pressure can be four times the absolute suction pressure. An example of a two-stage centrifugal compressor system, in this case for automotive applications, is described in U.S. Pat. No. 5,065,990, incorporated herein by reference.

The compositions of the present invention suitable for use in a refrigeration or air conditioning systems employing a centrifugal compressor comprise at least one of:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; -   1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; -   1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; -   1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; -   1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; -   1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; -   1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; -   2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; -   CF₃C(O)CBrFCF₂CF₃; -   CF₃C(O)CF₂CF₂CBrF₂; -   CBrF₂C(O)CF(CF₃)₂; -   CF₃C(O)CBr(CF₃)₂; -   CBrF₂CF₂C(O)CF₂CF₃; -   CF₃CBrFC(O)CF₂CF₃; -   CF₃CBrFC(O)CF₂CF₂CF₃; -   CF₃CF₂C(O)CBrFCF₂CF₃; -   CF₃CF₂C(O)CF₂CF₂CBrF₂; -   CF₃C(O)CBr(CF₃)CF₂CF₃; -   CF₃C(O)CF(CF₃)CBrFCF₃; -   CF₃C(O)CBrFCF₂CF₂CF₂CF₃; -   CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂; -   CF₃CBrFC(O)CF₂CF₂CF₂CF₃; -   CF₃CF₂C(O)CBrFCF₂CF₂CF₃; -   CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂; -   CF₃CF₂CBrFC(O)CF₂CF₂CF₃; -   CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃; -   CF₃CBrFC(O)CF(CF₃)CF₂CF₃; -   CF₃CF₂C(O)CBr(CF₃)CF₂CF₃; -   CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃; -   CBrF₂CF₂CF₂C(O)CF(CF₃)₂; -   CF₃CF₂CBrFC(O)CF(CF₃)₂; -   CF₃CF₂CF₂C(O)CBr(CF₃)₂; -   (CF₃)₂CBrC(O)CF(CF₃)₂; -   CF₃CBrFCF₂C(O)CF(CF₃)₂; -   CHF₂CF₂C(O)CBr(CF₃)₂; -   (CF₃)₂CHC(O)CBr(CF₃)₂; -   CHF₂CF₂C(O)CBrFCF₃; -   (CF₃)₂CHC(O)CBrFCF₃; -   (CF₃)₂CHC(O)CBrF₂; -   CBrF₂CF₂C(O)CH(CF₃)₂; -   CBrF₂C(O)CF(CF₃)OCF₃; -   CBrF₂CF₂C(O)CF(CF₃)OCF₃; -   CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃; -   CBrF₂C(O)CF(CF₃)OC₂F₅; -   CBrF₂CF₂C(O)CF(CF₃)OC₂F₅; -   CBrF₂C(O)CF(CF₃)OCF₂C₂F₅; -   CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅; -   CBrF₂C(O)CF(CF₃)OCF(CF₃)₂; -   CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂; -   CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; -   CF₃CBrFC(O)CF(CF₃)OCF₃; -   CF₃CBrFC(O)CF(CF₃)OC₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF₃; -   (CF₃)₂CBrC(O)CF(CF₃)OCF₃; -   CF₃CBrFC(O)CF(CF₃)OC₂F₅; -   (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; -   CBrF₂C(O)CF(OCF₂CHF₂)CF₃; -   CBrF₂C(O)CH(OCF₂CHF₂)CF₃; -   CBrF₂C(O)CF(OCH₃)CF₃; -   CBrF₂C(O)CF(CF₂OCH₃)CF₃; -   CClF₂CFBrC(O)CF₂CF₃; -   CBrF₂CFClC(O)CF₂CF₃; -   CClF₂CFBrC(O)CF(CF₃)₂; -   CBrF₂CFClC(O)CF(CF₃)₂; -   CClF₂CFBrC(O)CF(CF₃)(C₂F₅); -   CBrF₂CFClC(O)CF(CF₃)(C₂F₅); -   CClF₂C(O)CBr(CF₃)₂; -   CClF₂CF₂C(O)CBr(CF₃)₂; -   CF₃CClFC(O)CBr(CF₃)₂; -   CClF₂C(O)CBrFCF₃; -   CClF₂CF₂(O)CCBrFCF₃; -   CF₃CClFC(O)CBrFCF₃; -   CBrF₂C(O)CCl(CF₃)₂; -   CBrF₂CF₂C(O)CCl(CF₃)₂; -   CBrF₂C(O)CClFCF₃; -   CBrF₂CF₂C(O)CClFCF₃; or combinations thereof.

These above-listed compositions are also suitable for use in two-stage centrifugal compressor systems.

The compositions of the present invention may be used in stationary air-conditioning, heat pumps or mobile air-conditioning and refrigeration systems. Stationary air conditioning and heat pump applications include window, ductless, ducted, packaged terminal, chillers and commercial, including packaged rooftop. Refrigeration applications include domestic or home refrigerators and freezers, ice machines, self-contained coolers and freezers, walk-in coolers and freezers and transport refrigeration systems.

The compositions of the present invention may additionally be used in air-conditioning, heating and refrigeration systems that employ fin and tube heat exchangers, microchannel heat exchangers and vertical or horizontal single pass tube or plate type heat exchangers.

Conventional microchannel heat exchangers may not be ideal for the low pressure refrigerant compositions of the present invention. The low operating pressure and density result in high flow velocities and high frictional losses in all components. In these cases, the evaporator design may be modified. Rather than several microchannel slabs connected in series (with respect to the refrigerant path) a single slab/single pass heat exchanger arrangement may be used. Therefore, a preferred heat exchanger for the low pressure refrigerants of the present invention is a single slab/single pass heat exchanger.

The following compositions of the present invention are suitable for use in refrigeration or air conditioning systems employing a single slab/single pass heat exchanger:

-   1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; -   1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone -   1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; -   1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; -   1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; -   1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; -   1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; -   2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; -   CF₃C(O)CBrFCF₂CF₃; -   CF₃C(O)CF₂CF₂CBrF₂; -   CBrF₂C(O)CF(CF₃)₂; -   CF₃C(O)CBr(CF₃)₂; -   CBrF₂CF₂C(O)CF₂CF₃; -   CF₃CBrFC(O)CF₂CF₃; -   CF₃CBrFC(O)CF₂CF₂CF₃; -   CF₃CF₂C(O)CBrFCF₂CF₃; -   CF₃CF₂C(O)CF₂CF₂CBrF₂; -   CF₃C(O)CBr(CF₃)CF₂CF₃; -   CF₃C(O)CF(CF₃)CBrFCF₃; -   CF₃C(O)CBrFCF₂CF₂CF₂CF₃; -   CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂; -   CF₃CBrFC(O)CF₂CF₂CF₂CF₃; -   CF₃CF₂C(O)CBrFCF₂CF₂CF₃; -   CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂; -   CF₃CF₂CBrFC(O)CF₂CF₂CF₃; -   CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃; -   CF₃CBrFC(O)CF(CF₃)CF₂CF₃; -   CF₃CF₂C(O)CBr(CF₃)CF₂CF₃; -   CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃; -   CBrF₂CF₂CF₂C(O)CF(CF₃)₂; -   CF₃CF₂CBrFC(O)CF(CF₃)₂; -   CF₃CF₂CF₂C(O)CBr(CF₃)₂; -   (CF₃)₂CBrC(O)CF(CF₃)₂; -   CF₃CBrFCF₂C(O)CF(CF₃)₂; -   CHF₂CF₂C(O)CBr(CF₃)₂; -   (CF₃)₂CHC(O)CBr(CF₃)₂; -   CHF₂CF₂C(O)CBrFCF₃; -   (CF₃)₂CHC(O)CBrFCF₃; -   (CF₃)₂CHC(O)CBrF₂; -   CBrF₂CF₂C(O)CH(CF₃)₂; -   CBrF₂C(O)CF(CF₃)OCF₃; -   CBrF₂CF₂C(O)CF(CF₃)OCF₃; -   CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃; -   CBrF₂C(O)CF(CF₃)OC₂F₅; -   CBrF₂CF₂C(O)CF(CF₃)OC₂F₅; -   CBrF₂C(O)CF(CF₃)OCF₂C₂F₅; -   CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅; -   CBrF₂C(O)CF(CF₃)OCF(CF₃)₂; -   CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂; -   CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; -   CF₃CBrFC(O)CF(CF₃)OCF₃; -   CF₃CBrFC(O)CF(CF₃)OC₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF₃; -   (CF₃)₂CBrC(O)CF(CF₃)OCF₃; -   CF₃CBrFC(O)CF(CF₃)OC₂F₅; -   (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅; -   CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; -   CBrF₂C(O)CF(OCF₂CHF₂)CF₃; -   CBrF₂C(O)CH(OCF₂CHF₂)CF₃; -   CBrF₂C(O)CF(OCH₃)CF₃; -   CBrF₂C(O)CF(CF₂OCH₃)CF₃; -   CClF₂CFBrC(O)CF₂CF₃; -   CBrF₂CFClC(O)CF₂CF₃; -   CClF₂CFBrC(O)CF(CF₃)₂; -   CBrF₂CFClC(O)CF(CF₃)₂; -   CClF₂CFBrC(O)CF(CF₃)(C₂F₅); -   CBrF₂CFClC(O)CF(CF₃)(C₂F₅); -   CClF₂C(O)CBr(CF₃)₂; -   CClF₂CF₂C(O)CBr(CF₃)₂; -   CF₃CClFC(O)CBr(CF₃)₂; -   CClF₂C(O)CBrFCF₃; -   CClF₂CF₂(O)CCBrFCF₃; -   CF₃CClFC(O)CBrFCF₃; -   CBrF₂C(O)CCl(CF₃)₂; -   CBrF₂CF₂C(O)CCl(CF₃)₂; -   CBrF₂C(O)CClFCF₃; -   CBrF₂CF₂C(O)CClFCF₃; or combinations thereof.

The compositions of the present invention are particularly useful in small turbine centrifugal compressors, which can be used in auto and window air conditioning or heat pumps as well as other applications. These high efficiency miniature centrifugal compressors may be driven by an electric motor and can therefore be operated independently of the engine speed. A constant compressor speed allows the system to provide a relatively constant cooling capacity at all engine speeds. This provides an opportunity for efficiency improvements especially at higher engine speeds as compared to a conventional R-134a automobile air-conditioning system. When the cycling operation of conventional systems at high driving speeds is taken into account, the advantage of these low pressure systems becomes even greater.

Some of the low pressure refrigerant fluids of the present invention may be suitable as drop-in replacements for CFC-113 in existing centrifugal equipment.

The present invention relates to a process for producing refrigeration comprising evaporating the compositions of the present invention in the vicinity of a body to be cooled, and thereafter condensing said compositions.

The present invention further relates to a process for producing heat comprising condensing the compositions of the present invention in the vicinity of a body to be heated, and thereafter evaporating said compositions.

The present invention further relates to a process for transfer of heat from a heat source to a heat sink via a heat transfer fluid, wherein the compositions of the present invention serve as heat transfer fluids. Said process for heat transfer comprises transferring the compositions of the present invention from a heat source to a heat sink.

Heat transfer fluids are utilized to transfer, move or remove heat from one space, location, object or body to a different space, location, object or body by radiation, conduction, or convection. A heat transfer fluid may function as a secondary coolant by providing means of transfer for cooling (or heating) from a remote refrigeration (or heating) system. In some systems, the heat transfer fluid may remain in a constant state throughout the transfer process (i.e., not evaporate or condense). Alternatively, evaporative cooling processes may utilize heat transfer fluids as well.

A heat source may be defined as any space, location, object or body from which it is desirable to transfer, move or remove heat. Examples of heat sources may be spaces (open or enclosed) requiring refrigeration or cooling, such as refrigerator or freezer cases in a supermarket, building spaces requiring air conditioning, or the passenger compartment of an automobile requiring air conditioning. A heat sink may be defined as any space, location, object or body capable of absorbing heat. A vapor compression refrigeration system is one example of such a heat sink.

EXAMPLES Example 1 Tip Speed to Develop Pressure

Tip speed can be estimated by making some fundamental relationships for refrigeration equipment that use centrifugal compressors. The torque an impeller ideally imparts to a gas is defined as T=m*(v ₂ *r ₂ −v ₁ *r ₁)  Equation 1 where

T=torque, N*m

m=mass rate of flow, kg/s

v₂=tangential velocity of refrigerant leaving impeller (tip speed), m/s

r₂=radius of exit impeller, m

v₁=tangential velocity of refrigerant entering impeller, m/s

r₁=radius of inlet of impeller, m

Assuming the refrigerant enters the impeller in an essentially radial direction, the tangential component of the velocity v₁=0, therefore T=m*v ₂ *r ₂  Equation 2

The power required at the shaft is the product of the torque and the rotative speed P=T*w  Equation 3 where

P=power,W

w=rotative speed, rez/s

therefore, P=T*w=m*v ₂ *r ₂ *w  Equation 4

At low refrigerant flow rates, the tip speed of the impeller and the tangential velocity of the refrigerant are nearly identical; therefore r ₂ *w=v ₂  Equation 5 and P=m*v ₂ *v ₂  Equation 6

Another expression for ideal power is the product of the mass rate of flow and the isentropic work of compression, P=m*H _(i)*(1000 J/kJ)  Equation 7 where

H_(i)=Difference in enthalpy of the refrigerant from a saturated vapor at the evaporating conditions to saturated condensing conditions, kJ/kg.

Combining the two expressions Equation 6 and 7 produces, v ₂ *v ₂=1000*H _(i)  Equation 8

Although Equation 8 is based on some fundamental assumptions, it provides a good estimate of the tip speed of the impeller and provides an important way to compare tip speeds of refrigerants.

Table 3 below shows theoretical tip speeds that are calculated for 1,2,2-trichlorotrifluoroethane (CFC-113) and compositions of the present invention. The conditions assumed for this comparison are: Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0° F. (43.3° C.) Liquid subcool temperature 10.0° F. (5.5° C.) Return gas temperature 75.0° F. (23.8° C.) Compressor efficiency is 70%

These are typical conditions under which small turbine centrifugal compressors perform. TABLE 3 Hi Hi*0.7 Hi*0.7 V2 V2 rel Refrigerant (Btu/lb) (Btu/lb) (KJ/Kg) (m/s) to CFC-113 CFC-113 10.92 7.6 17.8 133.3 n/a PEIK 11.55 8.1 18.8 137.1 103% PMIK 10.94 7.7 17.8 133.5 100% CF₃C(O)CBrFCF₂CF₃ 9.9 6.9 16.1 127.0  95%

The data shows that compounds of the present invention have tip speeds within about +/−5 percent of CFC-113 and would be effective replacements for CFC-113 with minimal compressor design changes.

Example 2 Performance Data

Table 4 shows the performance of various refrigerants compared to CFC-113. The data are based on the following conditions. Evaporator temperature 40.0° F. (4.4° C.) Condenser temperature 110.0° F. (43.3° C.) Subcool temperature 10.0° F. (5.5° C.) Return gas temperature 75.0° F. (23.8° C.) Compressor efficiency is 70%

TABLE 4 Evap Evap Cond P Cond P Compr Compr Press Press Press Press Disch T Disch T Capacity Capacity Refrigerant (Psia) (kPa) (Psia) (kPa) (F.) (C.) COP (Btu/min) (kW) CFC-113 2.7 19 12.8 88 156.3 69.1 4.18 14.8 0.26 PEIK 2.2 15 12.5 86 124.6 51.4 3.73 13.4 0.24 PMIK 7.3 50 33.0 227 127.9 53.3 3.68 37.6 0.66 CF₃C(O)CBrFCF_(2—) 0.6 4 4.9 33 142.3 61.3 4.08 4.9 0.09 CF₃ Data show the compositions of the present invention have evaporator and condenser pressures similar to CFC-113. Some compositions also have higher capacity or energy efficiency (COP) than CFC-113. 

1. A haloketone refrigerant or heat transfer fluid composition said composition selected from the group consisting of: 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; CF₃C(O)CBrFCF₂CF₃; CF₃C(O)CF₂CF₂CBrF₂; CBrF₂C(O)CF(CF₃)₂; CF₃C(O)CBr(CF₃)₂; CBrF₂CF₂C(O)CF₂CF₃; CF₃CBrFC(O)CF₂CF₃; CF₃CBrFC(O)CF₂CF₂CF₃; CF₃CF₂C(O)CBrFCF₂CF₃; CF₃CF₂C(O)CF₂CF₂CBrF₂; CF₃C(O)CBr(CF₃)CF₂CF₃; CF₃C(O)CF(CF₃)CBrFCF₃; CF₃C(O)CBrFCF₂CF₂CF₂CF₃; CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂; CF₃CBrFC(O)CF₂CF₂CF₂CF₃; CF₃CF₂C(O)CBrFCF₂CF₂CF₃; CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂; CF₃CF₂CBrFC(O)CF₂CF₂CF₃; CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃; CF₃CBrFC(O)CF(CF₃)CF₂CF₃; CF₃CF₂C(O)CBr(CF₃)CF₂CF₃; CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)₂; CF₃CF₂CBrFC(O)CF(CF₃)₂; CF₃CF₂CF₂C(O)CBr(CF₃)₂; (CF₃)₂CBrC(O)CF(CF₃)₂; CF₃CBrFCF₂C(O)CF(CF₃)₂; CHF₂CF₂C(O)CBr(CF₃)₂; (CF₃)₂CHC(O)CBr(CF₃)₂; CHF₂CF₂C(O)CBrFCF₃; (CF₃)₂CHC(O)CBrFCF₃; (CF₃)₂CHC(O)CBrF₂; CBrF₂CF₂C(O)CH(CF₃)₂; CBrF₂C(O)CF(CF₃)OCF₃; CBrF₂CF₂C(O)CF(CF₃)OCF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃; CBrF₂C(O)CF(CF₃)OC₂F₅; CBrF₂CF₂C(O)CF(CF₃)OC₂F₅; CBrF₂C(O)CF(CF₃)OCF₂C₂F₅; CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅; CBrF₂C(O)CF(CF₃)OCF(CF₃)₂; CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF₃; CF₃CBrFC(O)CF(CF₃)OC₂F₅; CF₃CBrFC(O)CF(CF₃)OCF₃; (CF₃)₂CBrC(O)CF(CF₃)OCF₃; CF₃CBrFC(O)CF(CF₃)OC₂F₅; (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅; CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅; CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; CBrF₂C(O)CF(OCF₂CHF₂)CF₃; CBrF₂C(O)CH(OCF₂CHF₂)CF₃; CBrF₂C(O)CF(OCH₃)CF₃; CBrF₂C(O)CF(CF₂OCH₃)CF₃; CClF₂CFBrC(O)CF₂CF₃; CBrF₂CFClC(O)CF₂CF₃; CClF₂CFBrC(O)CF(CF₃)₂; CBrF₂CFClC(O)CF(CF₃)₂; CClF₂CFBrC(O)CF(CF₃)(C₂F₅); CBrF₂CFClC(O)CF(CF₃)(C₂F₅); CClF₂C(O)CBr(CF₃)₂; CClF₂CF₂C(O)CBr(CF₃)₂; CF₃CClFC(O)CBr(CF₃)₂; CClF₂C(O)CBrFCF₃; CClF₂CF₂(O)CCBrFCF₃; CF₃CClFC(O)CBrFCF₃; CBrF₂C(O)CCl(CF₃)₂; CBrF₂CF₂C(O)CCl(CF₃)₂; CBrF₂C(O)CClFCF₃; CBrF₂CF₂C(O)CClFCF₃; and combinations thereof.
 2. A refrigerant or heat transfer fluid composition suitable for use in refrigeration or air conditioning apparatus employing a centrifugal compressor, said composition selected from the group consisting of: 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; CF₃C(O)CBrFCF₂CF₃; CF₃C(O)CF₂CF₂CBrF₂; CBrF₂C(O)CF(CF₃)₂; CF₃C(O)CBr(CF₃)₂; CBrF₂CF₂C(—O)CF₂CF₃; CF₃CBrFC(O)CF₂CF₃; CF₃CBrFC(O)CF₂CF₂CF₃; CF₃CF₂C(O)CBrFCF₂CF₃; CF₃CF₂C(O)CF₂CF₂CBrF₂; CF₃C(O)CBr(CF₃)CF₂CF₃; CF₃C(O)CF(CF₃)CBrFCF₃; CF₃C(O)CBrFCF₂CF₂CF₂CF₃; CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂; CF₃CBrFC(O)CF₂CF₂CF₂CF₃; CF₃CF₂C(O)CBrFCF₂CF₂CF₃; CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂; CF₃CF₂CBrFC(O)CF₂CF₂CF₃; CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃; CF₃CBrFC(O)CF(CF₃)CF₂CF₃; CF₃CF₂C(O)CBr(CF₃)CF₂CF₃; CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)₂; CF₃CF₂CBrFC(O)CF(CF₃)₂; CF₃CF₂CF₂C(O)CBr(CF₃)₂; (CF₃)₂CBrC(O)CF(CF₃)₂; CF₃CBrFCF₂C(O)CF(CF₃)₂; CHF₂CF₂C(O)CBr(CF₃)₂; (CF₃)₂CHC(O)CBr(CF₃)₂; CHF₂CF₂C(O)CBrFCF₃; (CF₃)₂CHC(O)CBrFCF₃; (CF₃)₂CHC(O)CBrF₂; CBrF₂CF₂C(O)CH(CF₃)₂; CBrF₂C(O)CF(CF₃)OCF₃; CBrF₂CF₂C(O)CF(CF₃)OCF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃; CBrF₂C(O)CF(CF₃)OC₂F₅; CBrF₂CF₂C(O)CF(CF₃)OC₂F₅; CBrF₂C(O)CF(CF₃)OCF₂C₂F₅; CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅; CBrF₂C(O)CF(CF₃)OCF(CF₃)₂; CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF₃; CF₃CBrFC(O)CF(CF₃)OC₂F₅; CF₃CBrFC(O)CF(CF₃)OCF₃; (CF₃)₂CBrC(O)CF(CF₃)OCF₃; CF₃CBrFC(O)CF(CF₃)OC₂F₅; (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅; CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅; CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; CBrF₂C(O)CF(OCF₂CHF₂)CF₃; CBrF₂C(O)CH(OCF₂CHF₂)CF₃; CBrF₂C(O)CF(OCH₃)CF₃; CBrF₂C(O)CF(CF₂OCH₃)CF₃; CClF₂CFBrC(O)CF₂CF₃; CBrF₂CFClC(O)CF₂CF₃; CClF₂CFBrC(O)CF(CF₃)₂; CBrF₂CFClC(O)CF(CF₃)₂; CClF₂CFBrC(O)CF(CF₃)(C₂F₅); CBrF₂CFClC(O)CF(CF₃)(C₂F₅); CClF₂C(O)CBr(CF₃)₂; CClF₂CF₂C(O)CBr(CF₃)₂; CF₃CClFC(O)CBr(CF₃)₂; CClF₂C(O)CBrFCF₃; CClF₂CF₂(O)CCBrFCF₃; CF₃CClFC(O)CBrFCF₃; CBrF₂C(O)CCl(CF₃)₂; CBrF₂CF₂C(O)CCl(CF₃)₂; CBrF₂C(O)CClFCF₃; CBrF₂CF₂C(O)CClFCF₃; and combinations thereof.
 3. A refrigerant or heat transfer fluid composition suitable for use in refrigeration or air conditioning apparatus employing a multi-stage or centrifugal compressor or a single slab/single pass heat exchanger, said composition selected from the group consisting of: 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; CF₃C(O)CBrFCF₂CF₃; CF₃C(O)CF₂CF₂CBrF₂; CBrF₂C(O)CF(CF₃)₂; CF₃C(O)CBr(CF₃)₂; CBrF₂CF₂C(O)CF₂CF₃; CF₃CBrFC(O)CF₂CF₃; CF₃CBrFC(O)CF₂CF₂CF₃; CF₃CF₂C(O)CBrFCF₂CF₃; CF₃CF₂C(O)CF₂CF₂CBrF₂; CF₃C(O)CBr(CF₃)CF₂CF₃; CF₃C(O)CF(CF₃)CBrFCF₃; CF₃C(O)CBrFCF₂CF₂CF₂CF₃; CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂; CF₃CBrFC(O)CF₂CF₂CF₂CF₃; CF₃CF₂C(O)CBrFCF₂CF₂CF₃; CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂; CF₃CF₂CBrFC(O)CF₂CF₂CF₃; CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃; CF₃CBrFC(O)CF(CF₃)CF₂CF₃; CF₃CF₂C(O)CBr(CF₃)CF₂CF₃; CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)₂; CF₃CF₂CBrFC(O)CF(CF₃)₂; CF₃CF₂CF₂C(O)CBr(CF₃)₂; (CF₃)₂CBrC(O)CF(CF₃)₂; CF₃CBrFCF₂C(O)CF(CF₃)₂; CHF₂CF₂C(O)CBr(CF₃)₂; (CF₃)₂CHC(O)CBr(CF₃)₂; CHF₂CF₂C(O)CBrFCF₃; (CF₃)₂CHC(O)CBrFCF₃; (CF₃)₂CHC(O)CBrF₂; CBrF₂CF₂C(O)CH(CF₃)₂; CBrF₂C(O)CF(CF₃)OCF₃; CBrF₂CF₂C(O)CF(CF₃)OCF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃; CBrF₂C(O)CF(CF₃)OC₂F₅; CBrF₂CF₂C(O)CF(CF₃)OC₂F₅; CBrF₂C(O)CF(CF₃)OCF₂C₂F₅; CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅; CBrF₂C(O)CF(CF₃)OCF(CF₃)₂; CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF₃; CF₃CBrFC(O)CF(CF₃)OC₂F₅; CF₃CBrFC(O)CF(CF₃)OCF₃; (CF₃)₂CBrC(O)CF(CF₃)OCF₃; CF₃CBrFC(O)CF(CF₃)OC₂F₅; (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅; CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅; CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; CBrF₂C(O)CF(OCF₂CHF₂)CF₃; CBrF₂C(O)CH(OCF₂CHF₂)CF₃; CBrF₂C(O)CF(OCH₃)CF₃; CBrF₂C(O)CF(CF₂OCH₃)CF₃; CClF₂CFBrC(O)CF₂CF₃; CBrF₂CFClC(O)CF₂CF₃; CClF₂CFBrC(O)CF(CF₃)₂; CBrF₂CFClC(O)CF(CF₃)₂; CClF₂CFBrC(O)CF(CF₃)(C₂F₅); CBrF₂CFClC(O)CF(CF₃)(C₂F₅); CClF₂C(O)CBr(CF₃)₂; CClF₂CF₂C(O)CBr(CF₃)₂; CF₃CClFC(O)CBr(CF₃)₂; CClF₂C(O)CBrFCF₃; CClF₂CF₂(O)CCBrFCF₃; CF₃CClFC(O)CBrFCF₃; CBrF₂C(O)CCl(CF₃)₂; CBrF₂CF₂C(O)CCl(CF₃)₂; CBrF₂C(O)CClFCF₃; CBrF₂CF₂C(O)CClFCF₃; and combinations thereof.
 4. The composition of claim 3, wherein said composition is suitable for use in refrigeration or air conditioning apparatus employing a two-stage centrifugal compressor.
 5. A haloketone refrigerant or heat transfer fluid composition represented by the formula R³COR⁴, wherein R³ and R⁴ are independently selected from straight or branched chain, saturated or unsaturated, aliphatic or alicyclic fluorinated carbon radicals that may optionally contain hydrogen, chlorine, or bromine, and wherein R³ and R⁴ may optionally be joined to form a cyclic haloketone ring, and combinations of said haloketones represented by said formula.
 6. A composition according to claim 5, said composition selected from the group consisting of 1,1,1,2,2,4,5,5,5-nonafluoro-4-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,5,5,5-octafluoro-2,4-bis(trifluoromethyl)-3 pentanone; 1,1,1,2,4,4,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone; 1,1,1,2,4,4,5,5,6,6,6-undecafluoro-2-(trifluoromethyl)-3-hexanone; 1,1,2,2,4,5,5,5-octafluoro-1-(trifluoromethoxy)-4-(trifluoromethyl)-3-pentanone; 1,1,1,3,4,4,4-heptafluoro-3-(trifluoromethyl)-2-butanone; 1,1,1,2,2,5,5,5-octafluoro-4-(trifluoromethyl)-3-pentanone; and 2-chloro-1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-3-pentanone.
 7. The composition of claim 5, said composition comprising at least one brominated haloketone selected from the group consisting of monobromoperfluoroketones, monohydromonobromoperfluoroketones, perfluoroalkoxy)monobromoperfluoroketones, fluoroalkoxy)monobromoperfluoroketones, and monochloromonobromoperfluoroketones.
 8. The composition of claim 7, said composition comprising at least one selected from the group consisting of: CF₃C(O)CBrFCF₂CF₃; CF₃C(O)CF₂CF₂CBrF₂; CBrF₂C(O)CF(CF₃)₂; CF₃C(O)CBr(CF₃)₂; CBrF₂CF₂C(O)CF₂CF₃; CF₃CBrFC(O)CF₂CF₃; CF₃CBrFC(O)CF₂CF₂CF₃; CF₃CF₂C(O)CBrFCF₂CF₃; CF₃CF₂C(O)CF₂CF₂CBrF₂; CF₃C(O)CBr(CF₃)CF₂CF₃; CF₃C(O)CF(CF₃)CBrFCF₃; CF₃C(O)CBrFCF₂CF₂CF₂CF₃; CF₃C(O)CF₂CF₂CF₂CF₂CBrF₂; CF₃CBrFC(O)CF₂CF₂CF₂CF₃; CF₃CF₂C(O)CBrFCF₂CF₂CF₃; CF₃CF₂C(O)CF₂CF₂CF₂CBrF₂; CF₃CF₂CBrFC(O)CF₂CF₂CF₃; CBrF₂CF₂C(O)CF(CF₃)CF₂CF₃; CF₃CBrFC(O)CF(CF₃)CF₂CF₃; CF₃CF₂C(O)CBr(CF₃)CF₂CF₃; CF₃CF₂C(O)CF(CBrF₂)CF₂CF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)₂; CF₃CF₂CBrFC(O)CF(CF₃)₂; CF₃CF₂CF₂C(O)CBr(CF₃)₂; (CF₃)₂CBrC(O)CF(CF₃)₂; CF₃CBrFCF₂c(O)cF(CF₃)₂; CHF₂CF₂C(O)CBr(CF₃)₂; (CF₃)₂CHC(O)CBr(CF₃)₂; CHF₂CF₂C(O)CBrFCF₃; (CF₃)₂CHC(O)CBrFCF₃; (CF₃)₂CHC(O)CBrF₂; CBrF₂CF₂C(O)CH(CF₃)₂; CBrF₂C(O)CF(CF₃)OCF₃; CBrF₂CF₂C(O)CF(CF₃)OCF₃; CBrF₂CF₂CF₂C(O)CF(CF₃)OCF₃; CBrF₂C(O)CF(CF₃)OC₂F₅; CBrF₂CF₂C(O)CF(CF₃)OC₂F₅; CBrF₂C(O)CF(CF₃)OCF₂C₂F₅; CBrF₂CF₂C(O)CF(CF₃)OCF₂C₂F₅; CBrF₂C(O)CF(CF₃)OCF(CF₃)₂; CBrF₂CF₂C(O)CF(CF₃)OCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; CF₃CBrFC(O)CF(CF₃)OCF₃; CF₃CBrFC(O)CF(CF₃)OC₂F₅; CF₃CBrFC(O)CF(CF₃)OCF₃; (CF₃)₂CBrC(O)CF(CF₃)OCF₃; CF₃CBrFC(O)CF(CF₃)OC₂F₅; (CF₃)₂CBrC(O)CF(CF₃)OC₂F₅; CF₃CBrFC(O)CF(CF₃)OCF₂C₂F₅; CF₃CBrFC(O)CF(CF₃)OCF(CF₃)₂; CBrF₂C(O)CF(OCF₂CHF₂)CF₃; CBrF₂C(O)CH(OCF₂CHF₂)CF₃; CBrF₂C(O)CF(OCH₃)CF₃; CBrF₂C(O)CF(CF₂OCH₃)CF₃; CClF₂CFBrC(O)CF₂CF₃; CBrF₂CFClC(O)CF₂CF₃; CClF₂CFBrC(O)CF(CF₃)₂; CBrF₂CFClC(O)CF(CF₃)₂; CClF₂CFBrC(O)CF(CF₃)(C₂F₅); CBrF₂CFClC(O)CF(CF₃)(C₂F₅); CClF₂C(O)CBr(CF₃)₂; CClF₂CF₂C(O)CBr(CF₃)₂; CF₃CClFC(O)CBr(CF₃)₂; CClF₂C(O)CBrFCF₃; CClF₂CF₂(O)CCBrFCF₃; CF₃CClFC(O)CBrFCF₃; CBrF₂C(O)CCl(CF₃)₂; CBrF₂CF₂C(O)CCl(CF₃)₂; CBrF₂C(O)CClFCF₃; and CBrF₂CF₂C(O)CClFCF₃.
 9. A process for producing refrigeration, said process comprising evaporating the composition of claim 1, 2, 3, 4, or 5 in the vicinity of a body to be cooled, and thereafter condensing said composition.
 10. A process for producing heat, said process comprising condensing the composition of claim 1, 2, 3, 4, or 5 in the vicinity of a body to be heated, and thereafter evaporating said composition.
 11. A method of using the compositions of claim 1, 2, 3, 4, or 5 for heat transfer, said method comprising transferring said composition from a heat source to a heat sink.
 12. The composition of claim 1, further comprising ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.
 13. The composition of claim 2, 3, 4, or 5, further comprising at least one ultra-violet fluorescent dye selected from the group consisting of naphthalimides, perylenes, coumarins, anthracenes, phenanthracenes, xanthenes, thioxanthenes, naphthoxanthenes, fluoresceins, derivatives of said dye and combinations thereof.
 14. The composition of claim 12, further comprising at least one solubilizing agent selected from the group consisting of hydrocarbons, dimethylether, polyoxyalkylene glycol ethers, amides, ketones, nitriles, chlorocarbons, esters, lactones, aryl ethers, fluoroethers, and 1,1,1-trifluoroalkanes.
 15. The composition of claim 14, wherein said solubilizing agent is selected from the group consisting of: a) polyoxyalkylene glycol ethers represented by the formula R¹[(OR²)_(x)OR³]_(y), wherein: x is an integer from 1 to 3; y is an integer from 1 to 4; R¹ is selected from hydrogen and aliphatic hydrocarbon radicals having 1 to 6 carbon atoms and y bonding sites; R² is selected from aliphatic hydrocarbylene radicals having from 2 to 4 carbon atoms; R³ is selected from hydrogen, and aliphatic and alicyclic hydrocarbon radicals having from 1 to 6 carbon atoms; at least one of R¹ and R³ is selected from said hydrocarbon radicals; and wherein said polyoxyalkylene glycol ethers have a molecular weight of from about 100 to about 300 atomic mass units; b) amides represented by the formulae R¹CONR²R³ and cyclo-[R⁴CON(R⁵)—], wherein R¹, R², R³ and R⁵ are independently selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms, and at most one aromatic radical having from 6 to 12 carbon atoms; R⁴ is selected from aliphatic hydrocarbylene radicals having from 3 to 12 carbon atoms; and wherein said amides have a molecular weight of from about 100 to about 300 atomic mass units; c) ketones represented by the formula R¹COR², wherein R¹ and R² are independently selected from aliphatic, alicyclic and aryl hydrocarbon radicals having from 1 to 12 carbon atoms, and wherein said ketones have a molecular weight of from about 70 to about 300 atomic mass units; d) nitriles represented by the formula R¹CN, wherein R¹ is selected from aliphatic, alicyclic or aryl hydrocarbon radicals having from 5 to 12 carbon atoms, and wherein said nitriles have a molecular weight of from about 90 to about 200 atomic mass units; e) chlorocarbons represented by the formula RCl_(x), wherein; x is selected from the integers 1 or 2; R is selected from aliphatic and alicyclic hydrocarbon radicals having from 1 to 12 carbon atoms; and wherein said chlorocarbons have a molecular weight of from about 100 to about 200 atomic mass units; f) aryl ethers represented by the formula R¹OR², wherein: R¹ is selected from aryl hydrocarbon radicals having from 6 to 12 carbon atoms; R² is selected from aliphatic hydrocarbon radicals having from 1 to 4 carbon atoms; and wherein said aryl ethers have a molecular weight of from about 100 to about 150 atomic mass units; g) 1,1,1-trifluoroalkanes represented by the formula CF₃R¹, wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; i) fluoroethers represented by the formula R¹OCF₂CF₂H, wherein R¹ is selected from aliphatic and alicyclic hydrocarbon radicals having from about 5 to about 15 carbon atoms; and j) lactones represented by structures [B], [C], and [D]:

 wherein, R₁ through R₈ are independently selected from hydrogen, linear, branched, cyclic, bicyclic, saturated and unsaturated hydrocarbyl radicals; and the molecular weight is from about 100 to about 300 atomic mass units; and k) esters represented by the general formula R¹CO₂R², wherein R¹ and R² are independently selected from linear and cyclic, saturated and unsaturated, alkyl and aryl radicals; and wherein said esters have a molecular weight of from about 80 to about 550 atomic mass units.
 16. A method for using the composition of claim 12 or 14, said method comprising, (a) introducing the composition into a compression refrigeration or air conditioning apparatus by (i) dissolving the ultraviolet fluorescent dye in the refrigerant composition of heat transfer fluid in the presence of the solubilizing agent, and introducing the combination into said compression refrigeration or air conditioning apparatus or (ii), combining solubilizing agent and and UV flurorescent dye and introducing said combination into refrigeration or air conditioning apparatus containing refrigerant and/or heat transfer fluid.
 17. A method for using the composition of claim 12 or 14 in compression refrigeration ot air conditioning apparatus, said method comprising providing said composition to said apparatus, and providing a suitable means for detecting saif composition in the vicinity of said apparatus.
 18. A method of using the composition of claim 12 or 14, said method comprising: (i) producing refrigeration by evaporating said composition in the vicinity of a body to be cooled and thereafter condensing said composition; or (ii) producing heat by condensing said composition in the vicinity of the body to be heated and thereafter evaporation said composition.
 19. The composition of claim 11, further comprising an odor-masking agent, fragrance, or thermal stabilizer.
 20. The composition of claim 18, wherein the thermal stabilizer is nitromethane. 